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1. Rapid fabrication of interdigitated electrodes by laser ablation with application to electrokinetically enhanced surface plasmon resonance imaging

Author: Larry O'Connell, Brice Poirier, Oleksii Bratash, Charlène Plénière, Loïc Leroy, Yoann Roupioz, Pierre R. Marcoux, Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département Microtechnologies pour la Biologie et la Santé (DTBS), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Y spot, CEA Grenoble, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: [PHYS]Physics [physics], Fabrication, [SPI]Engineering Sciences [physics], Rapid prototyping, Anti-microbial peptides, Biosensing, Dielectrophoresis, Electrical and Electronic Engineering, Surface Plasmon Resonance, Atomic and Molecular Physics, and Optics, Laser ablation, Electronic, Optical and Magnetic Materials
Abstract: International audience; Significance: Dielectrophoresis, electro-osmosis, and other electrokinetic effects are frequently used in a variety of applications but necessitate patterning of electrodes on sensor surfaces. This typically requires a cleanroom and time-consuming, expensive, and arcane lithography and etching procedures.Aim: To demonstrate the applicability of commercial laser direct writing equipment for rapid patterning of electrodes into gold layers on glass substrates, particularly with application to producing electrokinetically active plasmonic sensors.Approach: A commercial printed circuit board prototyper was used to pattern interdigitated electrode (IDE) arrays into the surface of gold-coated slides and off-the-shelf surface plasmon resonance (SPR) prisms. The electrode geometries resulting from different patterning parameters were characterized by profilometry and electron microscopy. The patterned surfaces were then employed for trapping and electro-kinetic manipulation of bacteria, and finally for sensing of bacteria by SPR imaging.Results: Fabrication of an IDE array can be completed in as little as 12 s, with longer fabrication times permitting superior geometry and minimum feature size of 15 μm. The patterned IDEs were capable of concentrating bacteria and controlling their position on the sensor surface as a function of applied frequencies. SPR was demonstrated to detect specific interactions between bacteria and immobilized antimicrobial peptides.Conclusions: Laser direct writing is demonstrated as a feasible, cleanroom-free alternative to more lengthy lithography methods, permitting very rapid fabrication and prototyping of IDEs, which are compatible with active plasmonic sensing and bacterial detection.
Published: 2023

2. FeNC Oxygen Reduction Electrocatalyst with High Utilization Penta‐Coordinated Sites

Author: Jesús Barrio, Angus Pedersen, Saurav Ch. Sarma, Alexander Bagger, Mengjun Gong, Silvia Favero, Chang‐Xin Zhao, Ricardo Garcia‐Serres, Alain Y. Li, Qiang Zhang, Frédéric Jaouen, Frédéric Maillard, Anthony Kucernak, Ifan E. L. Stephens, Maria‐Magdalena Titirici, Imperial College London, Department of Chemistry [Imperial College London], Department of Chemical Engineering, Tsinghua University, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Bolin Centre for Climate Research, Stockholm University, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Electrochimie Interfaciale et Procédés (EIP), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), WPI Advanced Institute for Materials Research (WPI-AIMR), Tohoku University [Sendai], ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), European Project: 866402,NitroScission, European Project: 892614,HAEMOGLOBIN, and European Project: 896637 ,DimerCat
Subjects: Mechanics of Materials, Mechanical Engineering, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; Atomic Fe in N-doped carbon (FeNC) electrocatalysts for oxygen (O$_2$) reduction at the cathode of proton exchange membrane fuel cells (PEMFCs) are the most promising alternative to platinum-group-metal catalysts. Despite recent progress on atomic FeNC O$_2$ reduction, their controlled synthesis and stability for practical applications remains challenging. A two-step synthesis approach has recently led to significant advances in terms of Fe-loading and mass activity; however, the Fe utilisation remains low owing to the difficulty of building scaffolds with sufficient porosity that electrochemically exposes the active sites. Herein, we addressed this issue by coordinating Fe in a highly porous nitrogen doped carbon support (~3295 m$^2$ g$^{-1}$), prepared by pyrolysis of inexpensive 2,4,6triaminopyrimidine and a Mg$^{2+}$ salt active site template and porogen. Upon Fe coordination, a high electrochemical active site density of 2.54×10$^{19}$ sites g$_{FeNC}$$^{-1}$ and a record 52% FeN$_x$ electrochemical utilisation based on in situ nitrite stripping was achieved. The Fe single atoms are characterised pre-and post-electrochemical accelerated stress testing by aberration-corrected high-angle annular dark field scanning transmission electron microscopy, showing no Fe clustering. Moreover, ex situ X-ray absorption spectroscopy and low-temperature Mössbauer spectroscopy suggest the presence of penta-coordinated Fe sites, which were further studied by density functional theory calculations.
Published: 2023

3. Cross-Linking of Ru(II) Polypyridyl Complexes Bearing Pyrrole Moieties on TiO2 Nanoparticles to Enhance Light to Electricity Conversion

Author: Long Le-Quang, Anass Benayad, Jean-Marie Mouesca, Vincent Maurel, Jérôme Chauvin, SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Energy, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; Herein we report the synthesis, electrochemical and photophysical behaviors of TiO2/P-[Ru-pyr]2+ where a [Ru(bpy)3]2+ (bpy = 2,2’-bipyridine ) core bearing two pyrrole substituents on distinct bipyridines, and a phosphonic anchoring group are immobilized on TiO2 colloidal nanoparticles. Under visible light and in the presence of O2 as sacrificial electron scavenger, TiO2/[Ru-pyr]2+ was converted into a nanocomposite suprastructure TiO2/oligo(Ru-pyr) where [Ru(bpy)3]2+ units were linked together through pyrrole coupling reaction. The photo-induced charge separated state (e )TiO2/RuII-pyr+ was revealed by electron paramagnetic resonance (EPR) spectroscopy ((e )TiO2 signal). The oxidative coupling of pyrroles was ascertained by identifying the additional organic radical EPR signal with DFT calculations of pyrrole-derived oligomers, combined with X-ray photoelectron spectroscopy (XPS) results. TiO2/oligo(Ru-pyr) exhibited a higher rate of electron injection from [Ru(bpy)3]2+* to TiO¬2 than for colloidal nanoparticules without pyrrole denoted as TiO2/[Ru]2+. The composites were then electrophoretically deposited on a fluorine-doped tin oxide surface and tested as photoanodes. At a bias of 0.12 V. vs Ag/Ag+ 0.01 M, FTO/TiO2/oligo(Ru-pyr) in presence of tertiary amine as sacrificial electron donor, displayed a current density double that of FTO/TiO2/[Ru]2+ under similar condition. XPS confirmed the stability of [Ru(bpy)3]2+ photosensitizer core after the photopolymerization process, but a partial desorption was observed after the electrophoretic deposition.
Published: 2022

4. Electrode Integration of Synthetic Hydrogenase as Bioinspired and Noble Metal-Free Cathodes for Hydrogen Evolution

Author: Afridi Zamader, Bertrand Reuillard, Pierre Marcasuzaa, Antoine Bousquet, Laurent Billon, Jose Jorge Espí Gallart, Gustav Berggren, Vincent Artero, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Department of Materials Chemistry - The Angstrom Laboratory, Uppsala University, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eurecat - Centro Tecnológico de Catalunya, Université Grenoble Alpes (UGA), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and European Project: 765376,eSCALED
Subjects: hydrogen evolution, molecular electrocatalysis, [CHIM.POLY]Chemical Sciences/Polymers, life cycle assessment, carbon nanotubes, bioinspired polymer matrices, [CHIM]Chemical Sciences, General Chemistry, cycle assessment, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Catalysis, hydrogenase mimics
Abstract: International audience; Diiron complexes mimicking the H-cluster of [FeFe]-hydrogenases have been extensively studied as (electro-)catalysts for proton reduction under homogeneous conditions. The incorporation of such complexes as "active sites" within macromolecular scaffolds such as organic polymers is receiving increasing attention as this strategy allows controlling the environment, that is, the outer coordination sphere, around the molecular catalytic center, to tune its performance as well as its stability. Here, we report on the synthesis and characterization of a library of metallo-copolymers featuring a bioinspired diiron active site and internal proton relays based on a previous report [Brezinski et al. Angew. Chem. Int. Ed. 2018, 57, 11898-11902]. The polymers are further functionalized with various amounts of pyrene groups for efficient noncovalent anchoring onto multi-walled carbon nanotubes (MWNTs), enabling the preparation of molecularly engineered electrode materials. The addition of pyrene anchors resulted in improved activity and stability, with a pyrene loading of about similar to 8% corresponding to an optimized balance between polymer hydrophilicity and surface affinity. The best material displayed an average turnover frequency (TOFH2) of 4.3 +/- 0.6 s(-1) and a conservative turnover number for H-2 production (TONH2) of 3.1 +/- 0.4 x 10(5) after 20 h of continuous bulk electrolysis in aqueous conditions at 0.39 V overpotential. Interestingly, comparing such activities with an analogous diiron site deprived from polymeric scaffold revealed that latter could only show TONH2 of similar to 4 +/- 2 x 10(3) and TOFH2 of 0.06 +/- 0.02 s(-1) in 20 h under the same conditions. Post operando analysis of the modified electrodes suggests that electrode inactivation occurs via leaching of the diiron core from MWNT. In addition, a life cycle assessment was carried out to evaluate the performance of the engineered electrode materials not only from a technical perspective but also from an environmental point of view.
Published: 2023

5. Electro- and photochemical H2 generation by Co(II) polypyridyl-based catalysts bearing ortho-substituted pyridines

Author: Fiorella Lucarini, Jennifer Fize, Adina Morozan, Federico Droghetti, Euro Solari, Rosario Scopelliti, Marco Marazzi, Mirco Natali, Mariachiara Pastore, Vincent Artero, Albert Ruggi, Université de Fribourg = University of Fribourg (UNIFR), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Università degli Studi di Ferrara = University of Ferrara (UniFE), Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL)-Batochime, Institut des Sciences et Ingénierie Chimiques (ISIC), Ecole Polytechnique Fédérale de Lausanne (EPFL), Universidad de Alcalá - University of Alcalá (UAH), Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Swiss National Foundation (Grant 159716, FN 7359), University of Ferrara (FIR2021, FAR2022), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Fuel Technology, Renewable Energy, Sustainability and the Environment, Energy Engineering and Power Technology, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract: International audience; Cobalt(II) complexes featuring hexadentate amino-pyridyl ligands have been recently discovered as highly active catalysts for the Hydrogen Evolution Reaction (HER), whose high performance arises from the possibility to assist proton transfer processes via intramolecular routes involving detached pyridine units. With the aim of gaining insights in such catalytic routine, three new proton reduction catalysts based on amino-polypyridyl ligands are reported, focusing on substitution of the pyridine ortho- position. Especially, a carboxylate (C2) and two hydroxyl substituted pyridyl moieties (C3, C4) are introduced with the aim of promoting intramolecular proton transfer possibly enhancing the efficiency of the catalysts. Foot-of-the-wave and catalytic Tafel plot analyses have been utilized to benchmark the catalytic performances under electrochemical conditions in acetonitrile using trifluoroacetic acid as the proton source. In this respect, the cobalt complex C3 results as the fastest catalyst in the series, maximum turnover frequency (TOF) of 1.6 (± 0.5)x105 s-1, but at the expenses of large overpotentials. Mechanistic investigation by means of Density Functional Theory (DFT) suggest a typical ECEC mechanism (i.e. a sequence of reductions -E- and protonations -C- events) for all the catalysts, as previously envisioned for the parent unsubstituted complex C1. Interestingly, in the case of complexes C2, the catalytic route is triggered by initial protonation of the carboxylate group resulting in a less common (C)ECEC mechanism. The pivotal role of the hexadentate chelating ligand in providing internal proton relays to assist hydrogen elimination is further confirmed within this novel class of molecular catalysts, thus highlighting the relevance of a flexible polypyridine ligand in the design of efficient cobalt complexes for the HER. Photochemical studies in aqueous solution using [Ru(bpy)3]2+ (where bpy = 2,2’-bipyridine) as the sensitizer and ascorbate as the sacrificial electron donor support the superior performance of C3.
Published: 2023

6. Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Author: Afridi Zamader, Bertrand Reuillard, Jacques Pécaut, Laurent Billon, Antoine Bousquet, Gustav Berggren, Vincent Artero, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Uppsala University, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: molecular electrocatalysis, carbon nanotubes, hydrogenase mimic, Chemical Sciences, Organic Chemistry, [CHIM]Chemical Sciences, Kemi, General Chemistry, pyrene, Catalysis, hydrogen evolution reaction
Abstract: International audience; Surface integration of molecular catalysts inspired from the active sites of hydrogenase enzymes represents a promising route towards developing noble metal-free and sustainable technologies for H2 production. Efficient and stable catalyst anchoring is a key aspect to enable this approach. Herein, we report the preparation and electrochemical characterization of an original diironhexacarbonyl complex including two pyrene groups per catalytic unit in order to allow for its smooth integration, through π-interactions, onto multiwalled carbon nanotube-based electrodes. In this configuration, the grafted catalyst could reach turnover numbers for H2 production (TONH2) of up to 4±2×103 within 20 h of bulk electrolysis, operating at neutral pH. Post operando analysis of catalyst functionalized electrodes revealed the degradation of the catalytic unit occurred via loss of the iron carbonyl units, while the anchoring groups and most part of the ligand remained attached onto multiwalled carbon nanotubes.
Published: 2022

7. Ligand-Promoted Surface Solubilization of TiO2 Nanoparticles by the Enterobactin Siderophore in Biological Medium

Author: Jérôme Laisney, Mireille Chevallet, Caroline Fauquant, Camille Sageot, Yohann Moreau, Daniela Predoi, Nathalie Herlin-Boime, Colette Lebrun, Isabelle Michaud-Soret, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), National Institute of Materials Physics (NIMP), Romanian Academy of Sciences, Laboratoire Edifices Nanométriques (LEDNA), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), the CEA‐Toxicology Transversal Program through the NanoBioMet and NanoStress grants, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-11-LABX-0064,SERENADE,Vers une conception de nanomatériaux innovants, durables et sûrs(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Titanium, siderophore, titanium dioxide, Iron, nanoparticle, biological medium, Siderophores, [CHIM.MATE]Chemical Sciences/Material chemistry, Ligands, Biochemistry, Escherichia coli, Nanoparticles, Food Additives, enterobactin, ligand-promoted dissolution, E171, Molecular Biology
Abstract: Titanium dioxide nanoparticles (TiOsub2/sub-NPs) are increasingly used in consumer products for their particular properties. Even though TiOsub2/subis considered chemically stable and insoluble, studying their behavior in biological environments is of great importance to figure their potential dissolution and transformation. The interaction between TiOsub2/sub-NPs with different sizes and crystallographic forms (anatase and rutile) and the strong chelating enterobactin (bent/b) siderophore was investigated to look at a possible dissolution. For the first time, direct evidence of anatase TiOsub2/sub-NP surface dissolution or solubilization (i.e., the removal of Ti atoms located at the surface) in a biological medium by this siderophore was shown and the progressive formation of a hexacoordinated titanium-enterobactin (Ti-bent/b) complex observed. This complex was characterized by UV-visible and Fourier transform infrared (FTIR) spectroscopy (both supported by Density Functional Theory calculations) as well as electrospray ionization mass spectrometry (ESI-MS) and X-ray photoelectron spectroscopy (XPS). A maximum of ca. 6.3% of Ti surface atoms were found to be solubilized after 24 h of incubation, releasing Ti-bent/bcomplexes in the micromolar range that could then be taken up by bacteria in an iron-depleted medium. From a health and environmental point of view, the effects associated to the solubilization of the E171 TiOsub2/subfood additive in the presence of enterobactin and the entrance of the Ti-enterobactin complex in bacteria were questioned.
Published: 2022
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8. An early origin of iron–sulfur cluster biosynthesis machineries before Earth oxygenation

Author: Pierre Simon Garcia, Francesca D’Angelo, Sandrine Ollagnier de Choudens, Macha Dussouchaud, Emmanuelle Bouveret, Simonetta Gribaldo, Frédéric Barras, Adaptation au stress et Métabolisme chez les entérobactéries - Stress adaptation and metabolism in enterobacteria (SAMe), Université Paris Cité (UPCité)-Microbiologie Intégrative et Moléculaire (UMR6047), Institut Pasteur [Paris] (IP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut Pasteur [Paris] (IP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Biologie Évolutive de la Cellule Microbienne - Evolutionary Biology of the Microbial Cell, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), This project was supported by Institut Pasteur and CNRS and by grants from the ANR-10-LABX-62-IBEID, the LabEx ARCANE (ANR-11-LABX-0003–01) and the CBH- EUR-GS (ANR-17-EURE-0003)., We thank members of the SAMe and of the EBMC units for discussion., ANR-10-LABX-0062,IBEID,Integrative Biology of Emerging Infectious Diseases(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Iron-Sulfur Proteins, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, Ecology, Iron, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, [CHIM.CATA]Chemical Sciences/Catalysis, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Ecology, Evolution, Behavior and Systematics, Genome, Bacterial, Phylogeny, Sulfur
Abstract: International audience; Iron–sulfur (Fe–S) clusters are ubiquitous cofactors essential for life. It is largely thought that the emergence of oxygenic photosynthesis and progressive oxygenation of the atmosphere led to the origin of multiprotein machineries (ISC, NIF and SUF) assisting Fe–S cluster synthesis in the presence of oxidative stress and shortage of bioavailable iron. However, previous analyses have left unclear the origin and evolution of these systems. Here, we combine exhaustive homology searches with genomic context analysis and phylogeny to precisely identify Fe–S cluster biogenesis systems in over 10,000 archaeal and bacterial genomes. We highlight the existence of two additional and clearly distinct ‘minimal’ Fe–S cluster assembly machineries, MIS (minimal iron–sulfur) and SMS (SUF-like minimal system), which we infer in the last universal common ancestor (LUCA) and we experimentally validate SMS as a bona fide Fe–S cluster biogenesis system. These ancestral systems were kept in archaea whereas they went through stepwise complexification in bacteria to incorporate additional functions for higher Fe–S cluster synthesis efficiency leading to SUF, ISC and NIF. Horizontal gene transfers and losses then shaped the current distribution of these systems, driving ecological adaptations such as the emergence of aerobic lifestyles in archaea. Our results show that dedicated machineries were in place early in evolution to assist Fe–S cluster biogenesis and that their origin is not directly linked to Earth oxygenation.
Published: 2022

9. Lanthanide complexes (Gd$^{III}$ and Eu$^{III}$) based on a DOTA-TEMPO platform for redox monitoring via relaxivity

Author: Richard Barré, Damien Mouchel dit Leguerrier, Quentin Ruet, Lionel Fedele, Daniel Imbert, Véronique Martel‐Frachet, Pascal H. Fries, Jennifer K. Molloy, Fabrice Thomas, Département de Chimie Moléculaire - Electrochimie Moléculaire et Photochimie Rédox (DCM - EmPRE), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), École Pratique des Hautes Études (EPHE), Université Paris sciences et lettres (PSL), Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-17-CE07-0034,Co-lantha,Complexes de lanthanides comme sondes redox radicalaires(2017)
Subjects: redox, relaxivity, Organic Chemistry, nitroxide, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, gadolinium, contrast agent, Biochemistry
Abstract: International audience; Three lanthanide complexes (Ln=Gd, Eu) based on a DO3 A ([Ln(L$_1$)]) or DO2 A ([Ln(L$_{2-3}$)]$^+$) platform appended by a redox active TEMPO-based arm were prepared. Complex [Ln(L$_2$)]$^+$) shows an alkyne arm, offering the possibility of postfunctionalization by click reaction to yield [Ln(L$_3$)]$^+$). The complexes demonstrate a redox response whereby the hydroxylamine, nitroxide and oxoammonium forms of the arm can be obtained in turn. Luminescence measurements on the europium complexes support an octadentate (L$_1$, L$_3$) or heptadentate (L$_2$) chelation by the ligand, with one water molecule in the inner coordination sphere. The relaxivity was determined from 20 kHz to 30 MHz by fast-field cycling NMR. The three Gd-III complexes under their hydroxylamine form [Gd(L$_1$)] and [Gd(L$_{2-3}$)]$^+$) show $r_1$ values of 7.0, 5.1 and 5.0 mM$^{-1}$ s$^{-1}$ (30 KHz), which increase to 8.8, 5.5 and 6.1 mM$^{-1}$ s$^{-1}$ in the nitroxide form. The radical complexes are not toxic against M21 cell lines, at least up to 40 $\mu$M. By using EPR spectroscopy we establish that they do not penetrate the cells with the exception of [Eu(L$_2$)]$^+$.
Published: 2022

10. In Cellulo Mössbauer and EPR Studies Bring New Evidence to the Long‐Standing Debate on Iron–Sulfur Cluster Binding in Human Anamorsin

Author: Geneviève Blondin, Martin Clémancey, Lucia Banci, Francesca Camponeschi, Simone Ciofi-Baffoni, Sara Matteucci, University of Florence, Department of Chemistry and Magnetic Resonance Center (CERM), Consorzio Interuniversitario Risonanze Magnetiche di Metallo Proteine (CIRMMP), Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)-University of Bologna-Partenaires INRAE, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Department of Chemistry, University of Florence, ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Università degli Studi di Firenze = University of Florence (UniFI), and Università degli Studi di Siena = University of Siena (UNISI)-Università degli Studi di Firenze = University of Florence (UniFI)-University of Bologna/Università di Bologna-Partenaires INRAE
Subjects: Iron-Sulfur Proteins, anamorsin, Protein family, Stereochemistry, metalloproteins, Iron–sulfur cluster, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, 03 medical and health sciences, Spectroscopy, Mossbauer, chemistry.chemical_compound, in cellulo EPR spectroscopy, law, Mössbauer spectroscopy, Iron-sulfur cluster binding, Cluster (physics), Metalloprotein, Humans, in cellulo Mcssbauer spectroscopy, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Electron paramagnetic resonance, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, 010405 organic chemistry, Communication, Electron Spin Resonance Spectroscopy, Intracellular Signaling Peptides and Proteins, General Medicine, General Chemistry, Communications, iron-sulfur clusters, 0104 chemical sciences, chemistry, Iron–Sulfur Clusters, in cellulo Mössbauer spectroscopy, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Biogenesis, Protein Binding
Abstract: Human anamorsin is an iron–sulfur (Fe–S)‐cluster‐binding protein acting as an electron donor in the early steps of cytosolic iron–sulfur protein biogenesis. Human anamorsin belongs to the eukaryotic CIAPIN1 protein family and contains two highly conserved cysteine‐rich motifs, each binding an Fe–S cluster. In vitro works by various groups have provided rather controversial results for the type of Fe–S clusters bound to the CIAPIN1 proteins. In order to unravel the knot on this topic, we used an in cellulo approach combining Mössbauer and EPR spectroscopies to characterize the iron–sulfur‐cluster‐bound form of human anamorsin. We found that the protein binds two [2Fe–2S] clusters at both its cysteine‐rich motifs., A combined in cellulo Mössbauer‐ and EPR‐based approach is applied to address controversial aspects of Fe–S cluster‐binding properties of human anamorsin, a protein involved in the biogenesis of cytosolic [4Fe–4S] cluster‐binding proteins. We show that human anamorsin binds two [2Fe–2S] clusters in‐cell in two highly conserved cysteine‐rich motifs typical of the eukaryotic CIAPIN1 protein family, with different electron‐spin‐relaxation properties.
Published: 2021

11. An [FeFe]‐Hydrogenase Mimic Immobilized through Simple Physiadsorption and Active for Aqueous H 2 Production

Author: Marcello Gennari, Abhishek Dey, Lianke Wang, Estak Ahmed, Carole Duboc, Dibyajyoti Saha, Vincent Artero, Somdatta Ghosh Dey, Department of Chemical Sciences, Indian Association for the Cultivation of Science, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-16-CE92-0012,NiFemim,Catalyseurs bio-inspirés de l'hydrogénase à [NiFe] pour la production d'hydrogène.(2016), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)
Subjects: bio-inspired catalysts, Aqueous solution, H-2 evolution, 010405 organic chemistry, Chemistry, earth-abundant electrocatalysts, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Hydrogenase mimic, 010402 general chemistry, Electrocatalyst, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, heterogeneous electrochemistry, Simple (abstract algebra), Electrochemistry, electrocatalysis
Abstract: International audience; Mimicking hydrogenases with synthetic complexes is a promising strategy for the design of Earth-abundant electrocatalysts for H$_2$ evolution as alternative to platinum. Here, we describe a bio-inspired FeFe electrocatalyst, with a semi-bridging $\mu$-CO ligand, active and stable for H$_2$ evolution in acidic aqueous solutions after its physiadsorption onto carbon-based electrodes.
Published: 2021

12. Resorcinol-based hemiindigoid derivatives as human tyrosinase inhibitors and melanogenesis suppressors in human melanoma cells

Author: Brayan Roulier, Inbal Rush, Leticia M. Lazinski, Basile Pérès, Hamza Olleik, Guy Royal, Ayelet Fishman, Marc Maresca, Romain Haudecoeur, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Grenoble Alpes (UGA), Technion - Israel Institute of Technology [Haifa], ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-19-CE44-0002,EPIDERMIS,Vers des sondes et inhibiteurs conçus pour interagir avec hsTY : une voie vers la suppression de la mélanogénèse in vivo(2019)
Subjects: Hemiindigoid, Indanone, Pharmacology, Melanogenesis, [SDV]Life Sciences [q-bio], Organic Chemistry, Drug Discovery, [CHIM]Chemical Sciences, Aurone, human Tyrosinase, General Medicine, human Tyrosinase Hemiindigoid Melanogenesis Melanoma Aurone Indanone, Melanoma
Abstract: International audience; Human tyrosinase (hsTYR) catalyzes the key steps of melanogenesis, making it a privileged target for reducing melanin production in vivo. However, very few hsTYR inhibitors have been reported so far in the literature, whereas thousands of mushroom tyrosinase (abTYR) inhibitors are known. Yet, as these enzymes are actually very different, including at their active sites, there is an urgent need for new true hsTYR inhibitors in order to enable human-directed pharmacological and dermocosmetic applications without encountering the inefficiency and toxicity issues currently triggered by kojic acid or hydroquinone. Starting from the two most active compounds reported to date, i.e. a 2-hydroxypyridine-embedded aurone and thiamidol, we combined herein key structural elements and developed new nanomolar hsTYR inhibitors with cell-based activity. From a complete series of thirty-eight synthesized derivatives, excellent inhibition values were obtained for two compounds in both human melanoma cell lysates and purified hsTYR assays, and a promising improvement was observed in whole cell experiments.
Published: 2022

13. Kinetics of isothermal dumbbell exponential amplification: effects of mix composition on LAMP and its derivatives

Author: Maud Savonnet, Mathilde Aubret, Patricia Laurent, Yoann Roupioz, Myriam Cubizolles, Arnaud Buhot, Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département Microtechnologies pour la Biologie et la Santé (DTBS), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and European Project: ANR-11-LABX-0003-01
Subjects: Kinetics, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Molecular Diagnostic Techniques, loop mediated isothermal amplification (LAMP), isothermal dumbbell exponential amplification (IDEA), kinetic model, nucleic acids amplification, logistic function, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Clinical Biochemistry, DNA, General Medicine, Nucleic Acid Amplification Techniques
Abstract: International audience; Loop-mediated isothermal amplification (LAMP) is an exponential amplification method of DNA strands that is more and more used for its high performances. Thanks to its high sensitivity and selectivity, LAMP found numerous applications from the detection of pathogens or viruses through their genome amplification to its incorporation as an amplification strategy in protein or miRNA biomarker quantification. The LAMP method is composed of two stages: the first one consists in the transformation of the DNA strands into dumbbell structures formed of two stems and loops thanks to four primers; then, in the second stage, only two primers are required to amplify the dumbbells exponentially in numerous hairpins of increasing lengths. In this paper, we propose a theoretical framework to analyze the kinetics of the second stage of LAMP, the isothermal dumbbell exponential amplification (IDEA) as function of the physico-chemical parameters of the amplification reaction. Dedicated experiments validate the models. We believe these results may help the optimization of LAMP performances by reducing the number of experiments necessary to find the best parameters.
Published: 2022

14. A Pyrene‐Triazacyclononane Anchor Affords High Operational Stability for CO 2 RR by a CNT‐Supported Histidine‐Tagged CODH

Author: Umberto Contaldo, Mathieu Curtil, Julien Pérard, Christine Cavazza, Alan Le Goff, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), BioEnergie et Environnement (BEE), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Carbon Monoxide Dehydrogenase, Azamacrocycles, Pyrene, CO2 Reduction, Carbon Nanotubes, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, General Medicine, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Catalysis
Abstract: International audience; An original 1-acetato-4-(1-pyrenyl)-1,4,7-triazacyclononane (AcPyTACN) was synthesized for the immobilization of a His-tagged recombinant CODH from Rhodospirillum rubrum (RrCODH) on carbon-nanotube electrodes. The strong binding of the enzyme at the Ni-AcPyTACN complex affords a high current density of 4.9 mA cm$^{-2}$ towards electroenzymatic CO$_2$ reduction and a high stability of more than 6x10$^{6}$ TON when integrated on a gas-diffusion bioelectrode.
Published: 2022

15. A Combined Spectroscopic and Theoretical Study on a Ruthenium Complex Featuring a π‐Extended dppz Ligand for Light‐Driven Accumulation of Multiple Reducing Equivalents

Author: Carolin Müller, Alexander Schwab, Nicholas M. Randell, Stephan Kupfer, Benjamin Dietzek‐Ivanšić, Murielle Chavarot‐Kerlidou, Institute of Physical Chemistry, Friedrich Schiller, University Jena, Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena (IPHT), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Center for Energy and Environmental Chemistry (CEEC Jena), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-19-CE05-0044,PhotoAcc,Photo-accumulation de charge bio-inspirée : de la conception de nouveaux systèmes à l'optimisation de processus redox multi-électroniques d'intérêt(2019)
Subjects: Photosensitizing Agents, Ruthenium Photosensitizer, Spectrum Analysis, Organic Chemistry, General Chemistry, Models, Theoretical, Time-Resolved Spectroscopy, Ligands, Ruthenium, Catalysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Computational Chemistry, Artificial Photosynthesis, Multielectron Storage, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract: International audience; The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy)$_2$Ru(oxim-dppqp)]$^{2+}$ (Ru), storing two electrons coupled to two protons on the pi-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy)$_2$Ru(dppz)]$^{2+}$ and [(bpy)$_2$Ru(oxo-dppqp)]$^{2+}$ complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states.
Published: 2022

16. Cellular assays identify barriers impeding iron-sulfur enzyme activity in a non-native prokaryotic host

Author: Helena Shomar, Pierre Simon Garcia, Elena Fernández-Fueyo, Francesca D'Angelo, Martin Pelosse, Rita Rebelo Manuel, Ferhat Büke, Siyi Liu, Niels van den Broek, Nicolas Duraffourg, Carol de Ram, Martin Pabst, Emmanuelle Bouveret, Simonetta Gribaldo, Béatrice Py, Sandrine Ollagnier de Choudens, Frédéric Barras, Gregory Bokinsky, Adaptation au stress et Métabolisme chez les entérobactéries - Stress adaptation and metabolism in enterobacteria (SAMe), Université Paris Cité (UPCité)-Microbiologie Intégrative et Moléculaire (UMR6047), Institut Pasteur [Paris] (IP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut Pasteur [Paris] (IP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Kavli Institute of Nanosciences [Delft] (KI-NANO), Delft University of Technology (TU Delft), Biologie Évolutive de la Cellule Microbienne - Evolutionary Biology of the Microbial Cell, Biocatalyse (BIOCAT), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Laboratoire de chimie bactérienne (LCB), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Catalyse Bioinorganique et Environnement (BioCE ), This project (IRONPLUGNPLAY) has received funding from the European Union’s Horizon 2020 research and innovation programme under grant 722361 and was supported by grants from Agence Nationale Recherche (ANR): ANR-10-LABX-62-IBEID, the LabEx ARCANE (ANR-11-LABX-0003-01), and the CBH-EUR-GS (ANR-17-EURE-0003). Synthetic DNA prepared by the Joint Genome Institute DNA Synthesis Program was provided to GB (awarded proposal 503636). The work conducted by the U.S. Department of Energy Joint Genome Institute, a DOE Office of Science User Facility, is supported under Contract No. DE-AC02-05CH11231. SL was supported by the China Scholarship Council., ANR-10-LABX-0062,IBEID,Integrative Biology of Emerging Infectious Diseases(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and European Project: 722361,ERA CoBioTech
Subjects: Iron-Sulfur Proteins, General Immunology and Microbiology, Escherichia coli Proteins, Iron, infectious disease, General Neuroscience, microbiology, electron transfer protein, chemical biology, General Medicine, General Biochemistry, Genetics and Molecular Biology, [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, iron-sulfur enzyme, [SDV.MHEP.MI]Life Sciences [q-bio]/Human health and pathology/Infectious diseases, biochemistry, horizontal gene transfer, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, escherichia coli, microbial engineering, Phylogeny, Sulfur
Abstract: Iron-sulfur (Fe-S) clusters are ancient and ubiquitous protein cofactors and play irreplaceable roles in many metabolic and regulatory processes. Fe-S clusters are built and distributed to Fe-S enzymes by dedicated protein networks. The core components of these networks are widely conserved and highly versatile. However, Fe-S proteins and enzymes are often inactive outside their native host species. We sought to systematically investigate the compatibility of Fe-S networks with non-native Fe-S enzymes. By using collections of Fe-S enzyme orthologs representative of the entire range of prokaryotic diversity, we uncovered a striking correlation between phylogenetic distance and probability of functional expression. Moreover, coexpression of a heterologous Fe-S biogenesis pathway increases the phylogenetic range of orthologs that can be supported by the foreign host. We also find that Fe-S enzymes that require specific electron carrier proteins are rarely functionally expressed unless their taxon-specific reducing partners are identified and co-expressed. We demonstrate how these principles can be applied to improve the activity of a radical S-adenosyl methionine(rSAM) enzyme from a Streptomyces antibiotic biosynthesis pathway in Escherichia coli. Our results clarify how oxygen sensitivity and incompatibilities with foreign Fe-S and electron transfer networks each impede heterologous activity. In particular, identifying compatible electron transfer proteins and heterologous Fe-S biogenesis pathways may prove essential for engineering functional Fe-S enzyme-dependent pathways.
Published: 2022

17. A bidirectional bioinspired [FeFe]-hydrogenase model

Author: Md Estak Ahmed, Abhijit Nayek, Alenka Križan, Nathan Coutard, Adina Morozan, Somdatta Ghosh Dey, Reiner Lomoth, Leif Hammarström, Vincent Artero, Abhishek Dey, Indian Association for the Cultivation of Science, Uppsala University, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), This work was supported by the Indo-French Center for the Promotion of Advanced Research (IFCPAR/CEFIPRA Grant No. 5405-1), Department of Science and Technology, India, Grant DST/TMD/HFC/2K18/90., ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Iron-Sulfur Proteins, Colloid and Surface Chemistry, Hydrogenase, Catalytic Domain, Water, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Protons, Biochemistry, Catalysis, Hydrogen
Abstract: International audience; With the price-competitiveness of solar and wind power, hydrogen technologies may be game changers for a cleaner, defossilized, and sustainable energy future. H$_2$ can indeed be produced in electrolyzers from water, stored for long periods, and converted back into power, on demand, in fuel cells. The feasibility of the latter process critically depends on the discovery of cheap and efficient catalysts able to replace platinum group metals at the anode and cathode of fuel cells. Bioinspiration can be key for designing such alternative catalysts. Here we show that a novel class of iron-based catalysts inspired from the active site of [FeFe]-hydrogenase behave as unprecedented bidirectional electrocatalysts for interconverting H$_2$ and protons efficiently under near-neutral aqueous conditions. Such bioinspired catalysts have been implemented at the anode of a functional membrane-less H$_2$/O$_2$ fuel cell device.
Published: 2022

18. Structure and enzymatic degradation of the polysaccharide secreted by Nostoc commune

Author: Sophie Drouillard, Laurent Poulet, Eric Marechal, Alberto Amato, Laurine Buon, Mélanie Loiodice, William Helbert, Centre de Recherches sur les Macromolécules Végétales (CERMAV), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), LIPID, Physiologie cellulaire et végétale (LPCV), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), ANR-14-CE06-0017,1000Cazymes,Criblage fonctionnel de très divergentes, non-classées ou putatives enzymes de dégradation des polysaccharides(2014), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-20-CE02-0020,ALPALGA,Microalgues des Alpes(2020)
Subjects: Polysaccharide structure, Nostoc commune, Polysaccharides, Organic Chemistry, Enzymatic degradation, Carbohydrates, Oligosaccharides, Water, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, General Medicine, Biochemistry, NMR, Analytical Chemistry
Abstract: International audience; Noctoc commune is a cyanobacterium living in various and extreme environments. Its ability to survive in desert, on ice or high altitude is explained by its exceptional metabolism and its capacity to resist to desiccation. N. commune cells are embedded in a gelatinous matrix made of polysaccharides which fixes water and participates in maintaining the cells in hydrated conditions. The structure of the polysaccharide of N. commune harvested in Saint Martin d'Uriage (France) and the oligosaccharides obtained after its enzymatic degradation were determined. The repeating unit of the main chain is a tetra-saccharide: [→4)-β-D-Glcp-(1 → 4)-β-D-Xylp-(1 → 4)-β-D-Glcp-(1 → 4)-α-D-Galp-(1→], branched at position 6 of a glucose residue by a β-linked pyruvated glucuronic acid residue. About 30% of the Xylp residues were branched with a Xylf residue. Comparison of this structure with the polysaccharides secreted by other Nostoc species and strains suggest a strong selection pressure on the structure in agreement with its important biological role.
Published: 2022

19. Surfactant-like peptide self-assembled into hybrid nanostructures for electronic nose applications

Author: Jonathan S. Weerakkody, Marielle El Kazzy, Elise Jacquier, Pierre-Henri Elchinger, Raphael Mathey, Wai Li Ling, Cyril Herrier, Thierry Livache, Arnaud Buhot, Yanxia Hou, Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de biologie structurale (IBS - UMR 5075), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Aryballe Technologies, Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), ANR-18-CE42-0012,OBP-optinose,Des OBPs pour un Nez optoelectronique biomimetique(2018), ANR-10-LABX-0051,LANEF,Laboratory of Alliances on Nanosciences - Energy for the Future(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-10-INBS-0005,FRISBI,Infrastructure Française pour la Biologie Structurale Intégrée(2010), ANR-12-BS07-0017,GRAL,Une nouvelle Génération de dRogues pour la maladie d'ALzheimer basées sur des études in vitro et in silico des oligomères de la protéine beta-amyloide et des tests in vivo(2012), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: electronic nose, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, General Engineering, self-assembled monolayers, humidity, General Physics and Astronomy, Pulmonary Surfactants, Nanostructures, Surface-Active Agents, surfactant-like peptide, volatile organic compounds, surface plasmon resonance imaging, General Materials Science, Peptides, supramolecular structures
Abstract: International audience; An electronic nose (e-nose) utilizes a multisensor array, which relies on the vector contrast of combinatorial responses, to effectively discriminate between volatile organic compounds (VOCs). In recent years, hierarchical structures made of nonbiological materials have been used to achieve the required sensor diversity. With the advent of self-assembling peptides, the ability to tune nanostructuration, surprisingly, has not been exploited for sensor array diversification. In this work, a designer surfactant-like peptide sequence, CG$_7$–NH$_2$, is used to fabricate morphologically and physicochemically heterogeneous “biohybrid” surfaces on Au-covered chips. These multistructural sensing surfaces, containing immobilized hierarchical nanostructures surrounded by self-assembled monolayers, are used for the detection and discrimination of VOCs. Through a simple and judicious design process, involving changes in pH and water content of peptide solutions, a five-element biohybrid sensor array coupled with a gas-phase surface plasmon resonance imaging system is shown to achieve sufficient discriminatory capabilities for four VOCs. Moreover, the limit of detection of the multiarray system is bench-marked at
Published: 2022

20. Enantioselective approach for expanding the three‐dimensional space of tetrahydroquinoline to develop bet bromodomain inhibitors

Author: Marie‐Ange Lespinasse, Kaiyao Wei, Justine Perrin, Matthias Winkler, Sieme Hamaidia, Alexis Leroy, Zuzana Macek Jilkova, Christian Philouze, Patrice N. Marche, Carlo Petosa, Jérôme Govin, Anouk Emadali, Yung‐Sing Wong, Département de pharmacochimie moléculaire (DPM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institute for Advanced Biosciences / Institut pour l'Avancée des Biosciences (Grenoble) (IAB), Centre Hospitalier Universitaire [Grenoble] (CHU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Etablissement français du sang - Auvergne-Rhône-Alpes (EFS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut de biologie structurale (IBS - UMR 5075), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Centre Hospitalier Universitaire [Grenoble] (CHU), Département de Chimie Moléculaire (DCM), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-18-CE18-0007,InhiBET,Développement de nouvelles molécules antifongiques ciblant les protéines BET(2018), wong, yung-sing, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, CBH-EUR-GS - - CBH-EUR-GS2017 - ANR-17-EURE-0003 - EURE - VALID, and APPEL À PROJETS GÉNÉRIQUE 2018 - Développement de nouvelles molécules antifongiques ciblant les protéines BET - - InhiBET2018 - ANR-18-CE18-0007 - AAPG2018 - VALID
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, Stereoisomerism, Antineoplastic Agents, General Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, anti-inflammatory agent, Catalysis, tetrahydroquinoline, BET bromodomain inhibitor, Quinolines, za-ortho-quinone methide, organocatalysis
Abstract: International audience; The pharmaceutical industry has a pervasive need for chiral specific molecules with optimal affinity for their biological targets. However, the mass production of such compounds is currently limited by conventional chemical routes, that are costly and have an environmental impact. Here, we propose an easy access to obtain new tetrahydroquinolines, a motif found in many bioactive compounds, that is rapid and cost effective. Starting from simple raw materials, the procedure uses a proline-catalyzed Mannich reaction followed by the addition of BF3.OEt2, which generates a highly electrophilic aza-ortho-quinone methide intermediate capable of reacting with different nucleophiles to form the diversely functionalized tetrahydroquinoline. Moreover, this enantioselective one-pot process provides access for the first time to tetrahydroquinolines with a cis-2,3 and trans-3,4 configuration. As proof of concept, we demonstrate that a three-step reaction sequence, from simple and inexpensive starting compounds and catalysts, can generate a BD2-selective BET bromodomain inhibitor with anti-inflammatory effect.
Published: 2022

21. Optimum functionalization of Si nanowire FET for electrical detection of DNA hybridization

Author: R. Midahuen, B. Previtali, C. Fontelaye, G. Nonglaton, V. Stambouli, S. Barraud, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire des matériaux et du génie physique (LMGP ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: [PHYS]Physics [physics], Biosensing, DNA, silicon nanowire, Electrical and Electronic Engineering, ISFET, Electronic, Optical and Magnetic Materials, Biotechnology
Abstract: International audience; In this work, we demonstrate a wafer-scale fabrication of biologically sensitive Si nanowire FET for pH sensing and electrical detection of deoxyribonucleic acid (DNA) hybridization. Based on conventional "top-down" CMOS compatible technology, our bioFETs explore a wide range of design (nanowires (NW), nanoribbons (NR), and honeycomb (HC) structures) with opening access scaled down to only 120 nm. After device fabrication, I DS-V BG transfer and I DS-V DS output characteristics show a conventional n-type FET behavior with an I ON /I OFF value higher than 10 5 , as well as an increase of threshold voltage as the NW width is reduced. Then, using a capacitive coupling in our dually-gated Si bioFETs, the pH sensitivity is enhanced with a pH response up to 600 mV/pH. Finally, we successfully detected an increase of threshold voltage of n-type silicon nanowires (SiNWs) due to hybridized target DNA molecules.
Published: 2022

22. Copper Induces Protein Aggregation, a Toxic Process Compensated by Molecular Chaperones

Author: Lisa Zuily, Nora Lahrach, Rosi Fassler, Olivier Genest, Peter Faller, Olivier Sénèque, Yann Denis, Marie-Pierre Castanié-Cornet, Pierre Genevaux, Ursula Jakob, Dana Reichmann, Marie-Thérèse Giudici-Orticoni, Marianne Ilbert, Bioénergétique et Ingénierie des Protéines (BIP ), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), The Hebrew University of Jerusalem (HUJ), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Biologie Intégrative (CBI), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), University of Michigan [Ann Arbor], University of Michigan System, ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-19-CE44-0018,ChapCop,Rôle des protéines chaperons dans la survie bactérienne face à de fortes concentrations de cuivre(2019), Department of Biological Chemistry, The Alexander Silberman Institute of Life Sciences, The Hebrew University., Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut de Microbiologie de la Méditerranée (IMM), Department of Molecular, Cellular and Developmental Biology, University of Michigan, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Proteomics, proteostasis, Bacteria, copper tolerance, copper homeostasis, stress response, molecular chaperone, Microbiology, heat shock, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Anti-Bacterial Agents, protein aggregation, DnaK, copper stress, Protein Aggregates, [SDV.SP.MED]Life Sciences [q-bio]/Pharmaceutical sciences/Medication, Virology, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Escherichia coli, trigger factor, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], Reactive Oxygen Species, Copper, Molecular Chaperones
Abstract: International audience; Copper is well known for its antimicrobial and antiviral properties. Under aerobic conditions, copper toxicity relies in part on the production of reactive oxygen species (ROS), especially in the periplasmic compartment. However, copper is significantly more toxic under anaerobic conditions, in which ROS cannot be produced. This toxicity has been proposed to arise from the inactivation of proteins through mismetallations. Here, using the bacterium Escherichia coli, we discovered that copper treatment under anaerobic conditions leads to a significant increase in protein aggregation. In vitro experiments using E. coli lysates and tightly controlled redox conditions confirmed that treatment with Cu$^+$ under anaerobic conditions leads to severe ROS-independent protein aggregation. Proteomic analysis of aggregated proteins revealed an enrichment of cysteine- and histidine-containing proteins in the Cu$^+$-treated samples, suggesting that nonspecific interactions of Cu$^+$ with these residues are likely responsible for the observed protein aggregation. In addition, E. coli strains lacking the cytosolic chaperone DnaK or trigger factor are highly sensitive to copper stress. These results reveal that bacteria rely on these chaperone systems to protect themselves against Cu-mediated protein aggregation and further support our finding that Cu toxicity is related to Cu-induced protein aggregation. Overall, our work provides new insights into the mechanism of Cu toxicity and the defense mechanisms that bacteria employ to survive.
Published: 2022

23. Metal binding and oligomerization properties of FurC (PerR) from Anabaena sp. PCC7120: an additional layer of regulation?

Author: Cristina Sarasa-Buisan, Etienne Emonot, Marta Martínez-Júlvez, Emma Sevilla, Adrián Velázquez-Campoy, Serge Crouzy, M Teresa Bes, Isabelle Michaud-Soret, María F Fillat, Departamento de Bioquímica y Biología Molecular y Celular, University of Zaragoza - Universidad de Zaragoza [Zaragoza], Instituto de Biocomputación y Física de Sistemas Complejos = Institute for Biocomputation and Physics of Complex Systems (BIFI), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Chimie computationnelle, modélisation et rayons X (COMX), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Biocatalyse (BIOCAT), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010)
Subjects: Iron, Biophysics, PerR, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, reversible oxidation, Biochemistry, oligomerization, Biomaterials, Bacterial Proteins, metal-binding sites, metal catalyzed oxidation, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Disulfides, Sulfhydryl Compounds, Diamide, Manganese, Metals and Alloys, ferric uptake regulator FurC, Hydrogen Peroxide, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Anabaena, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Peroxides, Repressor Proteins, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dithiothreitol, Zinc, Chemistry (miscellaneous)
Abstract: Metal and redox homeostasis in cyanobacteria is tightly controlled to preserve the photosynthetic machinery from mismetallation and minimize cell damage. This control is mainly taken by FUR (ferric uptake regulation) proteins. FurC works as the PerR (peroxide response) paralog in Anabaena sp. PCC7120. Despite its importance, this regulator remained poorly characterized. Although FurC lacks the typical CXXC motifs present in FUR proteins, it contains a tightly bound zinc per subunit. FurC: Zn stoichiometrically binds zinc and manganese in a second site, manganese being more efficient in the binding of FurC: Zn to its DNA target PprxA. Oligomerization analyses of FurC: Zn evidence the occurrence of different aggregates ranging from dimers to octamers. Notably, intermolecular disulfide bonds are not involved in FurC: Zn dimerization, dimer being the most reduced form of the protein. Oligomerization of dimers occurs upon oxidation of thiols by H2O2 or diamide and can be reversed by 1,4-Dithiothreitol (DTT). Irreversible inactivation of the regulator occurs by metal catalyzed oxidation promoted by ferrous iron. However, inactivation upon oxidation with H2O2 in the absence of iron was reverted by addition of DTT. Comparison of models for FurC: Zn dimers and tetramers obtained using AlphaFold Colab and SWISS-MODEL allowed to infer the residues forming both metal-binding sites and to propose the involvement of Cys86 in reversible tetramer formation. Our results decipher the existence of two levels of inactivation of FurC: Zn of Anabaena sp. PCC7120, a reversible one through disulfide-formed FurC: Zn tetramers and the irreversible metal catalyzed oxidation. This additional reversible regulation may be specific of cyanobacteria.
Published: 2022

24. Functional exploration of the glycoside hydrolase family GH113

Author: Marie Couturier, Mélanie Touvrey-Loiodice, Nicolas Terrapon, Elodie Drula, Laurine Buon, Christine Chirat, Bernard Henrissat, William Helbert, Centre de Recherches sur les Macromolécules Végétales (CERMAV), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Architecture et fonction des macromolécules biologiques (AFMB), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Biodiversité et Biotechnologie Fongiques (BBF), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Laboratoire Génie des procédés papetiers (LGP2), Centre National de la Recherche Scientifique (CNRS)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), King Abdulaziz University, DTU Bioengineering, Department of Biotechnology and Biomedicine, Danmarks Tekniske Universitet = Technical University of Denmark (DTU)-Danmarks Tekniske Universitet = Technical University of Denmark (DTU), ANR-17-CARN-0025,CARN,ANR-17-CARN-0025, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Mannans, Multidisciplinary, Polysaccharide science, Glycoside Hydrolases, Hydrolases, Mannopyranoside, [SDV]Life Sciences [q-bio], beta-Mannosidase, Oligosaccharide interactions, Firmicutes, Mannose, Substrate Specificity
Abstract: β-Mannans are a heterogeneous group of polysaccharides with a common main chain of β-1,4-linked mannopyranoside residues. The cleavage of β-mannan chains is catalyzed by glycoside hydrolases called β-mannanases. In the CAZy database, β-mannanases are grouped by sequence similarity in families GH5, GH26, GH113 and GH134. Family GH113 has been under-explored so far with six enzymes characterized, all from the Firmicutes phylum. We undertook the functional characterization of 14 enzymes from a selection of 31 covering the diversity of the family GH113. Our observations suggest that GH113 is a family with specificity towards mannans, with variations in the product profiles and modes of action. We were able to assign mannanase and mannosidase activities to four out of the five clades of the family, increasing by 200% the number of characterized GH113 members, and expanding the toolbox for fine-tuning of mannooligosaccharides.
Published: 2022

25. Combining chemistry and topography to produce antifouling surfaces, a review

Author: Durand, Hippolyte, Whiteley, Amelia, Mailey, Pascal, Nonglaton, Guillaume, Département Microtechnologies pour la Biologie et la Santé (DTBS), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology
Abstract: International audience; Despite decades of research on the reduction of surface fouling from biomolecules like proteins or micro-organisms like bacteria, viruses or fungi, the ultimate antifouling surface remains undiscovered. Our strongly expanding, but still incomplete, understanding of micro-organisms interactions with surfaces, and biofilm formation partly impedes the development of fully biopassive surface treatments. In parallel, the recent covid-19 pandemic strengthened the crucial need for such treatments. Among the numerous approaches that are able to provide surfaces with antifouling properties, chemical, biological and topographical strategies have been implemented for instance in marine, medical or food industries. While chemical and biological approaches either prevent the non-specific adsorption of micro-organisms, or kill them, topographical strategies are often designed to generate a mechanical stress upon their membranes. Active Principle Ingredient (API) release can be efficient; however, as well as being limited in time, bioresistance is increasing and thus the use of antibiotics should be reconsidered. Therefore, reducing non-specific adsorption and limiting micro-organism attachment is necessary for long-term solutions. Bio-inspired strategies, combining both organic chemistry and topography, are currently at the heart of the best innovative and sustainable solutions. The simultaneous effect of micro/nano-structuration, together with engineered chemical or biological functionalization is believed to contribute to the development of ever-increasing antibiofouling surfaces. This review aims to present approaches combining hydrophobic or hydrophilic chemistry and structured surfaces to avoid biofouling in different fields of interest.
Published: 2022

26. Ratiometric luminescence detection of copper(I) by a resonant system comprising two antenna/lanthanide pairs

Author: Sergey A. Denisov, Didier Boturyn, Olivier Sénèque, Nathan D. McClenaghan, Céline Cepeda, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-12-BS07-0012,LUMZIF,Doigts de zinc luminescents : vers des sondes optiques proche-infrarouge basées sur les lanthanides pour l'imagerie biologique du zinc(2012), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)
Subjects: Lanthanide, Luminescence, Photoluminescence, chemistry.chemical_element, 010402 general chemistry, Photochemistry, Lanthanoid Series Elements, 01 natural sciences, Ion, Inorganic Chemistry, chemistry.chemical_compound, Coordination Complexes, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Naphthalene, Ions, Millisecond, Luminescent Agents, Molecular Structure, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Tryptophan, [SDV.BBM.BM]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Molecular biology, [CHIM.MATE]Chemical Sciences/Material chemistry, Probe, Copper, 0104 chemical sciences, chemistry, Luminescent Measurements, Peptide
Abstract: International audience; Selective and sensitive detection of Cu(I) is an ongoing challenge due to its important role in biological systems, for example. Herein, we describe a photoluminescent molecular chemosensor integrating two lanthanide ions (Tb$^{3+}$ and Eu$^{3+}$) and respective tryptophan and naphthalene antennas onto a polypeptide backbone. The latter was structurally inspired from copper-regulating biomacromolecules in Gram-negative bacteria and was found to bind Cu$^+$ effectively under pseudobiological conditions (log K$_{Cu}$$^+$ = 9.7 ± 0.2). Ion regulated modulation of lanthanide luminescence in terms of intensity and long, millisecond lifetime offers perspectives in terms of ratiometric and time-gated detection of Cu$^+$. The role of the bound ion in determining the photophysical properties is discussed with the aid of additional model compounds.
Published: 2021

27. Hydrogen Production at a NiO Photocathode Based on a Ruthenium Dye-Cobalt Diimine Dioxime Catalyst Assembly: Insights from Advanced Spectroscopy and Post-operando Characterization

Author: Didier Gasparutto, Benjamin Dietzek, Alexander Schwab, Murielle Chavarot-Kerlidou, Stephan Kupfer, Didier Léonard, Christine Saint-Pierre, Sebastian Bold, Nicolas Queyriaux, Jakob Bruhnke, Carolin Müller, Emmanouil Giannoudis, Vincent Artero, Dmitry Aldakov, Corinne Gablin, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena (IPHT), Center for Energy and Environmental Chemistry (CEEC Jena), Institut des Sciences Analytiques (ISA), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Institute of Physical Chemistry and Center for Energy and Environmental Chemistry Jena, (CEEC- Jena), Surfaces, Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institute for Physical Chemistry and Center for Energy and Environmental Chemistry, This work was supported by the European Commission's Seventh Framework Program (FP7/2007-2013) under grant agreement no. 306398 (FP7-IDEAS-ERC, Project PhotocatH2ode), the Deutsche Forschungsgemeinschaft (German Science Foundation, PHOTOACC project, grant no. KU 3933/2-1), and the French National Research Agency in the framework of the 'Investissements d'avenir' program (ANR15-IDEX-02, Labex ARCANE and CBH-EURGS, ANR-17EURE-0003) and the Franco-German University., ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), European Project: 306398,EC:FP7:ERC,ERC-2012-StG_20111012,PHOTOCATH2ODE(2012), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: dye-sensitized, Materials science, Hydrogen, solar fuels, Photoelectrochemistry, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Catalysis, Artificial photosynthesis, photoelectrochemistry, cobalt catalyst, General Materials Science, Hydrogen production, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Solar fuel, 0104 chemical sciences, Ruthenium, chemistry, 13. Climate action, hydrogen, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Water splitting, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; The production of hydrogen by efficient, low-cost, and integrated photoelectrochemical water splitting processes represents an important target for the ecological transition. This challenge can be addressed thanks to bioinspired chemistry and artificial photosynthesis approaches by designing dye-sensitized photocathodes for hydrogen production, incorporating bioinspired first-row transition metal-based catalysts. The present work r describes the preparation and photoelectrochemical characterization of a NiO photocathode sensitized with a phosphonate-derivatized ruthenium tris-diimine photosensitizer covalently linked to a cobalt diimine dioxime hydrogen-evolving catalyst. Under simulated AM 1.5G irradiation, hydrogen is produced with photocurrent densities reaching 84 +/- 7 mu A.cm(-2), which is among the highest values reported so far for dye-sensitized photocathodes with surface-immobilized catalysts. Thanks to the unique combination of advanced spectroscopy and surface characterization techniques, the fast desorption of the dyad from the NiO electrode and the low yield of electron transfer to the catalyst, resulting in the Co demetallation from the diimine dioxime framework, were identified as the main barriers limiting the performances and the stability of the system. This work therefore paves the way for a more rational design of molecular photocathodes for solar fuel production and represents a further step toward the development of sustainable processes for the production of hydrogen from sunlight and water.
Published: 2021

28. Approaching industrially relevant current densities for hydrogen oxidation with a bioinspired molecular catalytic material

Author: Edmond Gravel, Vincent Artero, Bertrand Reuillard, Pascale Chenevier, Jérémy Schild, Eric Doris, Adina Morozan, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and European Project: 779366,CRESCENDO
Subjects: 010405 organic chemistry, Chemistry, Hydrogen oxidation, General Chemistry, Carbon nanotube, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, 0104 chemical sciences, Active layer, law.invention, Anode, Colloid and Surface Chemistry, Chemical engineering, law, Energy transformation, Current (fluid), Current density
Abstract: International audience; Integration of efficient platinum-group-metal (PGM)-free catalysts to fuel cells and electrolyzers is a prerequisite to their large-scale deployment. Here, we describe the development of a molecular-based anode for the hydrogen oxidation reaction (HOR) through noncovalent integration of a DuBois type Ni bioinspired molecular catalyst at the surface of a carbon nanotube modified gas diffusion layer. This mild immobilization strategy enabled us to gain high control over the loading in catalytic sites. Additionally, through the adjustment of the hydration level of the active layer, a new record current density of 214 ± 20 mA cm$^{–2}$ could be reached at 0.4 V vs RHE with the PGM-free anode, at 25 °C. Near industrially relevant current densities were obtained at 55 °C with 150 ± 20 and 395 ± 30 mA cm$^{–2}$ at 0.1 and 0.4 V overpotentials, respectively. These results further demonstrate the relevance of such molecular approaches for the development of electrocatalytic platforms for energy conversion.
Published: 2021

29. Physico-Chemical Transformation and Toxicity of Multi-Shell InP Quantum Dots under Simulated Sunlight Irradiation, in an Environmentally Realistic Scenario

Author: Fanny Dussert, Géraldine Sarret, Karl David Wegner, Olivier Proux, Gautier Landrot, Pierre-Henry Jouneau, Peter Reiss, Marie Carrière, Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie (CIBEST ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Institut des Sciences de la Terre (ISTerre), Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Gustave Eiffel-Université Grenoble Alpes (UGA), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Météo-France, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), the Atomic Energy and Alternative Energies Commission (CEA) and the French Environment and Energy Management Agency (ADEME)., ANR-11-LABX-0064,SERENADE,Vers une conception de nanomatériaux innovants, durables et sûrs(2011), ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-10-LABX-0051,LANEF,Laboratory of Alliances on Nanosciences - Energy for the Future(2010), ANR-10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), and ANR-18-CE09-0039,FLUO,Synthèse en flux continu de quantum dots à base d'InP(2018)
Subjects: EXAFS, General Chemical Engineering, environmental degradation, [SDE]Environmental Sciences, quantum dot, indium, safer-by-design, toxicity, [CHIM]Chemical Sciences, General Materials Science
Abstract: Quantum dots (QDs) are widely used in optoelectronics, lighting, and photovoltaics leading to their potential release into the environment. The most promising alternative to the highly toxic cadmium selenide (CdSe) QDs are indium phosphide (InP) QDs, which show reduced toxicity and comparable optical and electronic properties. QD degradation leads to the release of toxic metal ions into the environment. Coating the QD core with robust shell(s) composed of another semi-conductor material enhances their properties and protects the QD from degradation. We recently developed double-shelled InP QDs, which proved to be less toxic than single-shell QDs. In the present study, we confirm their reduced cytotoxicity, with an LC50 at 77 nM for pristine gradient shell QDs and >100 nM for pristine thin and thick shell QDs. We also confirm that these three QDs, when exposed to simulated sunlight, show greater cytotoxicity compared to pristine ones, with LC50 ranging from 15 to 23 nM. Using a combination of spectroscopic and microscopic techniques, we characterize the degradation kinetics and transformation products of single- and double-shell QDs, when exposed to solar light at high temperature, simulating environmental conditions. Non-toxic pristine QDs degrade to form toxic In–phosphate, In–carboxylate, Zn–phosphate, and oxidized Se, all of which precipitate as heterogeneous deposits. Comparison of their degradation kinetics highlights that the QDs bearing the thickest ZnS outer shell are, as expected, the most resistant to photodegradation among the three tested QDs, as gradient shell, thin shell, and thick shell QDs lose their optical properties in less than 15 min, 60 min, and more than 90 min, respectively. They exhibit the highest photoluminescence efficiency, i.e., the best functionality, with a photoluminescence quantum yield in aqueous solution of 24%, as compared to 18% for the gradient shell and thin shell QDs. Therefore, they can be considered as safer-by-design QDs.
Published: 2022

30. LEAFY protein crystals with a honeycomb structure as a platform for selective preparation of outstanding stable bio-hybrid materials

Author: Sylvie Kieffer-Jaquinod, Philippe Carpentier, Stéphane Ravanel, Renaud Dumas, Julien Pérard, Olivier Hamelin, Stéphane Ménage, Alice Gogny, David Cobessi, Lucile Chiari, Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Biocatalyse (BIOCAT), European Synchrotron Radiation Facility (ESRF), Etude de la dynamique des protéomes (EDyP), BioSanté (UMR BioSanté), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), BioEnergie et Environnement (BEE), Plantes, Stress & Métaux (MetalStress), Physiologie cellulaire et végétale (LPCV), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), Institut de biologie structurale (IBS - UMR 5075), Régulateurs du développement de la fleur (Flo_RE ), 80|PRIME Program (CNRS), DRF Impulsion program (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-10-INBS-0008,ProFI,Infrastructure Française de Protéomique(2010), GON, Nathalie, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, Grenoble Alliance for Integrated Structural Cell Biology - - GRAL2010 - ANR-10-LABX-0049 - LABX - VALID, and Infrastructure Française de Protéomique - - ProFI2010 - ANR-10-INBS-0008 - INBS - VALID
Subjects: Materials science, chemistry.chemical_element, Nanotechnology, 010402 general chemistry, 01 natural sciences, Mass Spectrometry, symbols.namesake, Honeycomb, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, General Materials Science, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Leafy, Enzymatic digestion, 010405 organic chemistry, Ginkgo biloba, Proteins, [PHYS.COND.CM-MS] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0104 chemical sciences, Ruthenium, Plant Leaves, Honeycomb structure, chemistry, symbols, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Raman spectroscopy, Hybrid material, Protein crystallization, Chromatography, Liquid
Abstract: International audience; Well-organized protein assemblies offer many properties that justify their use for the design of innovative bionanomaterials. Herein, crystals of the oligomerization domain of the LEAFY protein from Ginkgo biloba, organized in a honeycomb architecture, were used as a modular platform for the selective grafting of a ruthenium-based complex. The resulting bio-hybrid crystalline material was fully characterized by UV-visible and Raman spectroscopy and by mass spectrometry and LC-MS analysis after selective enzymatic digestion. Interestingly, insertion of complexes within the tubular structure affords an impressive increase in stability of the crystals, eluding the use of stabilizing cross-linking strategies.
Published: 2021

31. Access to Metal Centers and Fluxional Hydride CoordinationIntegral for CO2 Insertion into [Fe3(μ-H)3]3+ Clusters

Author: Vincent J. Catalano, Dae Ho Hong, Jason Shearer, Leslie J. Murray, Ricardo B. Ferreira, Ricardo Garcia-Serres, Center for Catalysis, Department of Chemistry, University of Florida, University of Florida [Gainesville] (UF), Florida Center for Heterocyclic Chemistry, Department of Chemistry, University of Florida, Department of Chemistry, University of Nevada, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Department of Chemistry, Trinity University, Trinity University, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Tris, Steric effects, 010405 organic chemistry, Hydride, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Solvent, Metal, chemistry.chemical_compound, Crystallography, chemistry, visual_art, Kinetic isotope effect, visual_art.visual_art_medium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, Physical and Theoretical Chemistry, Cyclophane
Abstract: International audience; CO$_2$ insertion into tri(mu-hydrido) triiron(II) clusters ligated by a tris($\beta$-diketiminate) cyclophane is demonstrated to be balanced by sterics for CO$_2$ approach and hydride accessibility. Time-resolved NMR and UV-vis spectra for this reaction for a complex in which methoxy groups border the pocket of the hydride donor (Fe$_3$H$_3$L$^{OMe/Me}$, 4) result in a decreased activation barrier and increased kinetic isotope effect consistent with the reduced sterics. For the ethyl congener Fe$_3$H$_3$L$^{Et/Me}$(2), no correlation is found between rate and reaction solvent or added Lewis acids, implying CO$_2$ coordination to an Fe center in the mechanism. The estimated hydricity (50 kcal/mol) based on observed H/D exchange with BD$_3$ requires Fe-O bond formation in the product to offset an endergonic CO$_2$ insertion. $\mu_3$-hydride coordination is noted to lower the activation barrier for the first CO$_2$ insertion event in DFT calculations
Published: 2021

32. Efficient Electrochemical CO2/CO Interconversion by an Engineered Carbon Monoxide Dehydrogenase on a Gas-Diffusion Carbon Nanotube-Based Bioelectrode

Author: Julien Pérard, Clara Rinaldi, Christine Cavazza, Bruno Guigliarelli, Umberto Contaldo, Alan Le Goff, BioEnergie et Environnement (BEE), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA ), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Bioénergétique et Ingénierie des Protéines (BIP ), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and Département de Chimie Moléculaire - Bioélectrochimie pour les capteurs, l’énergie et les nanomatériaux (DCM - BioCEN)
Subjects: medicine.medical_specialty, bioelectrocatalysis, Inorganic chemistry, carbon monoxide dehydrogenase, Overpotential, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, medicine, [PHYS]Physics [physics], biology, carbon nanotubes, 010405 organic chemistry, Chemistry, Rhodospirillum rubrum, Active site, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, biology.organism_classification, 0104 chemical sciences, Turnover number, Bioelectrochemistry, biology.protein, nickel enzymes, EPR, Carbon monoxide dehydrogenase, CO2 RR
Abstract: International audience; Carbon monoxide dehydrogenase catalyzes the reversible oxidation of CO to CO2. The monofunctional enzyme from Rhodospirillum rubrum (RrCODH) has been extensively characterized in the past, although its use and investigation by bioelectrochemistry have been limited. Here, we developed a heterologous system yielding a highly stable and active recombinant RrCODH in one-step purification, with CO oxidation activity reaching a maximum of 26 500 U.mg(-1), making RrCODH the most active CODH under ambient conditions described so far. Electron paramagnetic resonance was used to precisely characterize the recombinant RrCODH, demonstrating the integrity of the active site. Selective CO2/CO interconversion with maximum turnover frequencies of 150 s(-1) for CO oxidation (1.5 mA cm(-2) at 250 mV overpotential) and 420 s(-1) for CO2 reduction (4.2 mA cm(-2) at 180 mV overpotential) is catalyzed by the recombinant RrCODH immobilized on MWCNT electrodes modified with 1-pyrenebutyric acid adamantyl amide (MWCNTADA), either in a classic three-electrode cell or in specifically designed CO2/CO-diffusing electrodes. This functional device is stable for hours with a turnover number of at least 800 000. The performances of recombinant RrCODH-modified MWCNTADA are close to the best metal-based and molecular-based catalysts. These results greatly increase the benchmark for bioelectrocatalysis of reversible CO2 conversion.
Published: 2021

33. Chimeric Protein–Protein Interface Inhibitors Allow Efficient Inhibition of Type III Secretion Machinery and Pseudomonas aeruginosa Virulence

Author: Rossimiriam Pereira de Freitas, Yung-Sing Wong, Aline Thomas, Sophie Plé, Younes Bouzidi, Antoine Fortuné, Caroline Barette, Flaviane Francisco Hilário, Ina Attrée, Marie-Odile Fauvarque, Tuan-Dung Ngo, Eric Faudry, Pathogenèse bactérienne et réponses cellulaires (PBRC), Biologie du Cancer et de l'Infection (BCI ), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Département de pharmacochimie moléculaire (DPM ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Genetics and Chemogenomics (GenChem), Laboratoire de Biologie à Grande Échelle (BGE - UMR S1038), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Universidade Federal de Minas Gerais [Belo Horizonte] (UFMG), Universidade Federal de Ouro Preto (UFOP), Associations 'Vaincre la mucoviscidose' and 'Gregory Lemarchand', AVIESAN T3SS (ANR PRP1.4), GIS-IBiSA and ChemBioFrance, Froggy platform of the CIMENT infrastructure (https://ciment.ujf-grenoble.fr), which is supported by the Rhône-Alpes region (GRANT CPER07_13 CIRA), ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-15-CE11-0018,HemoPseudo,Pneumonie hémorragique à Pseudomonas aeruginosa : étude de nouvelles stratégies de virulence(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), ANR-10-EQPX-0029,EQUIP@MESO,Equipement d'excellence de calcul intensif de Mesocentres coordonnés - Tremplin vers le calcul petaflopique et l'exascale(2010), Faudry, Eric, Grenoble Alliance for Integrated Structural Cell Biology - - GRAL2010 - ANR-10-LABX-0049 - LABX - VALID, Pneumonie hémorragique à Pseudomonas aeruginosa : étude de nouvelles stratégies de virulence - - HemoPseudo2015 - ANR-15-CE11-0018 - AAPG2015 - VALID, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, CBH-EUR-GS - - CBH-EUR-GS2017 - ANR-17-EURE-0003 - EURE - VALID, Innovative strategies for observing and modelling natural systems - - OSUG@20202010 - ANR-10-LABX-0056 - LABX - VALID, Equipements d'excellence - Equipement d'excellence de calcul intensif de Mesocentres coordonnés - Tremplin vers le calcul petaflopique et l'exascale - - EQUIP@MESO2010 - ANR-10-EQPX-0029 - EQPX - VALID, Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: 0301 basic medicine, [SDV]Life Sciences [q-bio], Protein subunit, 030106 microbiology, Virulence, hybrid molecules, medicine.disease_cause, Type three secretion system, Microbiology, 03 medical and health sciences, medicine, antivirulence, Secretion, biology, protein−protein interface inhibitors, Chemistry, Toxin, Pseudomonas aeruginosa, bacterial resistance, biology.organism_classification, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Fusion protein, Type III secretion system, 030104 developmental biology, Infectious Diseases, click chemistry, [SDV.MP.BAC] Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, Bacteria
Abstract: International audience; Pseudomonas aeruginosa (P. aeruginosa) is an opportunistic pathogen naturally resistant to many common antibiotics and acquires new resistance traits at an alarming pace. Targeting the bacterial virulence factors by an antivirulence strategy, therefore, represents a promising alternative approach besides antibiotic therapy. The Type III secretion system (T3SS) of P. aeruginosa is one of its main virulence factors. It consists of more than 20 proteins building a complex syringe-like machinery enabling the injection of toxin into host cells. Previous works showed that disrupting interactions between components of this machinery efficiently lowers the bacterial virulence. Using automated target-based screening of commercial and in-house libraries of small molecules, we identified compounds inhibiting the protein-protein interaction between PscE and PscG, the two cognate chaperones of the needle subunit PscF of P. aeruginosa T3SS. Two hits were selected and assembled using Split/Mix/Click chemistry to build larger hybrid analogues. Their efficacy and toxicity were evaluated using phenotypic analysis including automated microscopy and image analysis. Two nontoxic hybrid leads specifically inhibited the T3SS and reduced the ex vivo cytotoxicity of bacteria and their virulence in Galleria mellonella.
Published: 2019

34. Towards eco-friendly power sources: In series connected glucose biofuel cells power a disposable ovulation test

Author: Caroline Abreu, Yannig Nedellec, Alan Le Goff, Serge Cosnier, Olivier Ondel, Michael Holzinger, François Buret, Ampère, Département Bioingénierie (BioIng), Ampère (AMPERE), École Centrale de Lyon (ECL), Université de Lyon-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-École Centrale de Lyon (ECL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Ampère, Département Energie Electrique (EE), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Région Auvergne-Rhône-AlpesPlate-forme Chimie NanoBio http://icmg.ujf-grenoble.fr/ICMG-SITE/ICMG/index.php?page=ICMG-SITE/IC, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Battery (electricity), Materials science, Ovulation test, [SDV]Life Sciences [q-bio], Disposable device, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, In series connected stack, Automotive engineering, Stack (abstract data type), Materials Chemistry, Electrical and Electronic Engineering, Eco-Friendly power source, Instrumentation, [SDE.IE]Environmental Sciences/Environmental Engineering, Open-circuit voltage, [SPI.NRJ]Engineering Sciences [physics]/Electric power, Metals and Alloys, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Environmentally friendly, Enzymatic glucose biofuel cells, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Power (physics), Biofuel, 0210 nano-technology, Voltage drop, Biofuel Cells
Abstract: International audience; A disposable ovulation test is operated using a flow stack of 5 in series connected glucose biofuel cells giving an open circuit voltage (OCV) of 3.5 V. Such tests consume at total around 60 μWh of energy and in average 1.7 mW of power during one run of around 12 min which are supplied by a CR1220 3 V lithium button battery in the commercialized device. We replaced this battery by the glucose biofuel cell stack and observed during the measurements and display steps peak currents up to 1.4 mA inducing a voltage drop down to 2.8 V during few seconds (4 mW of power consumption). Even such power peaks are supported by the presented biofuel cell stack assuring the necessary operational cell voltage and current. After the measurements towards Luteinizing Hormone (LH) detection the display remains turned on for 8 min and consumes just 2 μW which allows to reestablish the initial OCV and to run a further test. The presented results demonstrate as proof of concept the suitability of eco-friendly enzymatic glucose biofuel cells as alternative power source for disposable devices.
Published: 2018

35. Self-Assembly of a Ginkgo Oligomerization Domain Creates a Sub-10-nm Honeycomb Architecture on Carbon and Silicon Surfaces with Customizable Pores: Implications for Nanoelectronics, Biosensing, and Biocatalysis

Author: Gregory Si Larbi, Denis Mariolle, Emmanuel Thévenon, François Parcy, Pierre-Henri Elchinger, Renaud Dumas, Pierre-Henri Jouneau, Denis Falconet, Raluca Tiron, Elise Jacquier, Régulateurs du développement de la fleur (Flo_RE ), Physiologie cellulaire et végétale (LPCV), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), LIPID, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), CEA program Nanoprot 3D, DRF impulsion grant, ANR-10-LABX-0049,GRAL,Grenoble Alliance for Integrated Structural Cell Biology(2010), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Materials science, Silicon, chemistry.chemical_element, Honeycomb (geometry), Nanotechnology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Domain (software engineering), Nanoelectronics, chemistry, Biocatalysis, General Materials Science, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Self-assembly, 0210 nano-technology, Biosensor, Carbon, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2021

36. Iron Oxidation in Escherichia coli Bacterioferritin Ferroxidase Centre, a Site Designed to React Rapidly with H2O2 but Slowly with O$_2$

Author: Martin Clémancey, Marina Lučić, Dimitri A. Svistunenko, Nick E. Le Brun, Jonathan A. R. Worrall, Geoffrey R. Moore, Michael T. Wilson, Geneviève Blondin, Jacob Pullin, Justin M. Bradley, University of Essex, Physiochimie des Métaux (PMB), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), University of East Anglia [Norwich] (UEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Models, Molecular, Metalloproteins | Hot Paper, Photochemistry, medicine.disease_cause, Peroxide, 01 natural sciences, law.invention, chemistry.chemical_compound, law, Electron paramagnetic resonance, Research Articles, 0303 health sciences, biology, Mössbauer spectroscopy, Ceruloplasmin, Bacterioferritin, General Medicine, Oxidation-Reduction, Research Article, EPR spectroscopy, inorganic chemicals, Iron, Radical, Mossbauer spectroscopy, 010402 general chemistry, Catalysis, fast kinetics, 03 medical and health sciences, Bacterial Proteins, Escherichia coli, medicine, ferroxidase center, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 030304 developmental biology, 010405 organic chemistry, fungi, Hydrogen Peroxide, General Chemistry, Cytochrome b Group, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, 0104 chemical sciences, Oxygen, A-site, chemistry, Ferritins, biology.protein, rapid freeze-quenching, Stoichiometry
Abstract: Both O2 and H2O2 can oxidize iron at the ferroxidase center (FC) of Escherichia coli bacterioferritin (EcBfr) but mechanistic details of the two reactions need clarification. UV/Vis, EPR, and Mössbauer spectroscopies have been used to follow the reactions when apo‐EcBfr, pre‐loaded anaerobically with Fe2+, was exposed to O2 or H2O2. We show that O2 binds di‐Fe2+ FC reversibly, two Fe2+ ions are oxidized in concert and a H2O2 molecule is formed and released to the solution. This peroxide molecule further oxidizes another di‐Fe2+ FC, at a rate circa 1000 faster than O2, ensuring an overall 1:4 stoichiometry of iron oxidation by O2. Initially formed Fe3+ can further react with H2O2 (producing protein bound radicals) but relaxes within seconds to an H2O2‐unreactive di‐Fe3+ form. The data obtained suggest that the primary role of EcBfr in vivo may be to detoxify H2O2 rather than sequester iron., The kinetics of E. coli bacterioferritin di‐ferrous ferroxidase centre reacting with O2 and H2O2 shows that H2O2 reacts circa 1000 times faster than O2 implying that the primary in vivo role of the protein is ROS detoxification rather than iron sequestering.
Published: 2021

37. Exploring Coumarins Reduction: NaBH 4 /MeOH versus Nickel Boride Generated In Situ

Author: Catherine Belle, Amaury du Moulinet d'Hardemare, Clarisse Faure, Hélène Jamet, Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: In situ, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 010402 general chemistry, Coumarin, 01 natural sciences, 0104 chemical sciences, Reduction (complexity), chemistry.chemical_compound, chemistry, Chemoselectivity, Nuclear chemistry, Nickel boride
Abstract: International audience; The role of reagents NaBH4/MeOH and nickel boride (Ni2B)generated in situ from NaBH4 and NiCl2, are compared in thereduction process of coumarin and a variety of 3,7-substitutedcoumarins bearing electro-donating (ED-group) or electro-withdrawinggroups (EW-group). Coumarins (chromen-2-ones) areonly reduced by Ni2B to the cyclic chromanones. This providesa useful and very simple reduction method for electron-richcoumarins, which are resistant to many other reducingmethods. DFT calculations underlined the role of substituentselectronic effects in the reactivity. Subsequent methanolysismay open the ring to methyl phenylpropanoate esters andalcohols resulting from their reductions can also be produced.
Published: 2020

38. Ditopic Chelators of Dicopper Centers for Enhanced Tyrosinases Inhibition

Author: Christian Philouze, Elina Buitrago, Lylia Challali, Marc Maresca, Elisabetta Bergantino, Ahcène Boumendjel, Marius Réglier, Marcello Carotti, Luigi Bubacco, Catherine Belle, Clarisse Faure, Hélène Jamet, Renaud Hardré, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Università degli Studi di Padova = University of Padua (Unipd), Département de pharmacochimie moléculaire (DPM), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universita degli Studi di Padova
Subjects: bioinorganic chemistry, copper active sites, ditopic inhibitors, docking, tyrosinases, Chelating Agents, Enzyme Inhibitors, Humans, Structure-Activity Relationship, Agaricales, Monophenol Monooxygenase, Stereochemistry, Tyrosinase, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Melanin, chemistry.chemical_compound, Moiety, Chelation, [CHIM.COOR]Chemical Sciences/Coordination chemistry, chemistry.chemical_classification, biology, 010405 organic chemistry, Organic Chemistry, Active site, General Chemistry, 0104 chemical sciences, Enzyme, chemistry, Docking (molecular), biology.protein, Kojic acid
Abstract: International audience; Tyrosinase enzymes (Tys) are involved in the key steps of melanin (protective pigments) biosynthesis and molecules targeting the binuclear copper active site on tyrosinases represent a relevant strategy to regulate enzyme activities. In this work, we studied the possible synergic effect generated by combination of known inhibitors. For this, derivatives containing kojic acid (KA) and 2-Hydroxypyridine-N-oxide (HOPNO) combined with a thiosemicarbazone (TSC) moiety were synthetized. Their inhibition activities were evaluated on purified tyrosinases from different sources (mushroom, bacterial and human) as well as on melanin production by lysates from human melanoma MNT-1 cell line. Results showed significant enhancement of the inhibitory effects compared to the parent compounds, in particular for HOPNO-TSC. In order to elucidate the interaction mode with the dicopper(II) active site, we investigated the binding studies towards a tyrosinase bio-inspired model of the dicopper(II) center. The structure of the isolated adduct between one ditopic inhibitor (KA-TSC) and the model complex reveals that the binding to a dicopper center can occur with both chelating sites. Computational studies on model complexes and docking studies on enzymes led to the identification of KA and HOPNO moieties as interacting groups with the dicopper active site.
Published: 2020

39. Distinct genetic bases for plant root responses to lipo-chitooligosaccharide signal molecules from distinct microbial origins

Author: Magali Garcia, Christophe Jacquet, Maxime Bonhomme, Sébastien Fort, Guillaume Bécard, Emilie Amblard, Fabienne Maillet, Sandra Bensmihen, Virginie Puech-Pagès, Sylvain Cottaz, Clare Gough, Olivier André, Centre de Recherches sur les Macromolécules Végétales (CERMAV), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire de Recherche en Sciences Végétales (LRSV), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire des Interactions Plantes Microbes Environnement (LIPME), Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS), ANR-14-CE18-0008,NICE CROPS,Bio-stimulateurs chitiniques naturels pour une agriculture durable(2014), ANR-11-INBS-0010,METABOHUB,Développement d'une infrastructure française distribuée pour la métabolomique dédiée à l'innovation(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), ANR-16-CRNT-0005,Innovation Chimie Carnot,Innovation Chimie Carnot(2016), and ANR-10-LABX-0041,TULIP,Towards a Unified theory of biotic Interactions: the roLe of environmental(2010)
Subjects: 0106 biological sciences, [SDV]Life Sciences [q-bio], Genome-wide association study, Nod, 01 natural sciences, lateral root development, Rhizobia, [SDV.GEN.GPL]Life Sciences [q-bio]/Genetics/Plants genetics, 03 medical and health sciences, lipo-chitooligosaccharides, Medicago truncatula, GWAS, [CHIM]Chemical Sciences, Legume, 030304 developmental biology, Genetics, 0303 health sciences, biology, fungi, Plant root, food and beverages, [SDV.BV.BOT]Life Sciences [q-bio]/Vegetal Biology/Botanics, Heritability, biology.organism_classification, Phenotype, [SDV.MP]Life Sciences [q-bio]/Microbiology and Parasitology, Nod Factors, 010606 plant biology & botany
Abstract: SummaryLipo-chitooligosaccharides (LCOs) were originally found as symbiotic signals called Nod Factors (Nod-LCOs) controlling nodulation of legumes by rhizobia. More recently LCOs were also found in symbiotic fungi and, more surprisingly, very widely in the kingdom fungi including in saprophytic and pathogenic fungi. The LCO-V(C18:1, Fuc/MeFuc), hereafter called Fung-LCOs, are the LCO structures most commonly found in fungi. This raises the question of how legume plants, such asMedicago truncatula, can perceive and discriminate between Nod-LCOs and these Fung-LCOs.To address this question, we performed a Genome Wide Association Study on 173 natural accessions ofMedicago truncatula, using a root branching phenotype and a newly developed local score approach.Both Nod- and Fung-LCOs stimulated root branching in most accessions but there was very little correlation in the ability to respond to these types of LCO molecules. Moreover, heritability of root response was higher for Nod-LCOs than for Fung-LCOs. We identified 123 loci for Nod-LCO and 71 for Fung-LCO responses, but only one was common.This suggests that Nod- and Fung-LCOs both control root branching but use different molecular mechanisms. The tighter genetic constraint of the root response to Fung-LCOs possibly reflects the ancestral origin of the biological activity of these molecules.
Published: 2020

40. Evolution and Plasticity of the Transcriptome Under Temperature Fluctuations in the Fungal Plant Pathogen Zymoseptoria tritici

Author: Arnaud Le Rouzic, Anne Genissel, Arthur J. Jallet, BIOlogie et GEstion des Risques en agriculture (BIOGER), AgroParisTech-Université Paris-Saclay-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Maladies infectieuses et vecteurs : écologie, génétique, évolution et contrôle (MIVEGEC), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD [France-Sud]), Univ Paris Saclay, CNRS, IRD, UMR Evolut Genomes Comportement & Ecol, Gif Sur Yvette, France, Academia fellowship, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Evolution, génomes, comportement et écologie (EGCE), and Institut de Recherche pour le Développement (IRD)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: 0106 biological sciences, Transposable element, Microbiology (medical), lcsh:QR1-502, RNA-Seq, Biology, 010603 evolutionary biology, 01 natural sciences, Genome, Microbiology, lcsh:Microbiology, Transcriptome, 03 medical and health sciences, Gene expression, experimental evolution, Gene, Original Research, 030304 developmental biology, Abiotic component, 0303 health sciences, Phenotypic plasticity, Experimental evolution, adaptive evolution, 030306 microbiology, fluctuation, Robustness (evolution), temperature, Evolutionary biology, plasticity, [SDE]Environmental Sciences, gene expression, Adaptation, RNA-seq
Abstract: – Background. Species are subjected to variable environment in nature. While the ability to cope with changes has been studied through theoretical approaches, the small number of empirical studies limits our understanding of the evolutionary molecular mechanisms underlying adaptation to fluctuations – Results. Whole transcriptome sequencing of the fungal wheat pathogen Zymoseptria tritici revealed the evolution of gene expression after 48 weeks of experimental evolution under stable or fluctuating temperature. We found that although there is a strong genetic signature of gene expression, fluctuating regime could have a large and pervasive effect on the transcriptome evolution. Results show a few hot spots of significantly differentially expressed genes in the genome, in regions enriched with transposable elements (TE), including on dispensable chromosomes. Further, our results evidenced gene evolution towards robustness associated with the fluctuating regime, suggesting robustness is adaptive in changing environment. Last, an analysis on gene expression correlation revealed a significant set of genes that could act as trans-regulators. – Conclusions. This study is the first evolve and re-sequence experiment of a fungal pathogen, with the goal to describe the potential ability to evolve to changing environment and the molecular changes occurring in response to fluctuating selection. In addition to explore the evolutionary potential of the pathogen under temperature fluctuation this work highlights the important role of transcriptional rewiring that can adjust regulation of cell growth and multiplication.
Published: 2020

41. A Mechanistic Rationale Approach Revealed the Unexpected Chemoselectivity of an Artificial Ru-Dependent Oxidase: A Dual Experimental/Theoretical Approach

Author: David Michael Mayes, Sarah Lopez, Chloé Leprêtre, Yohann Moreau, Christine Cavazza, Stéphane Ménage, Caroline Marchi-Delapierre, Serge Crouzy, Nicolai Burzlaff, Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique (DCM - SeRCO), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Groupe modélisation et chimie théorique (MCT ), Biocatalyse (BIOCAT), Friedrich-Alexander Universität Erlangen-Nürnberg (FAU), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), ANR-14-CE06-0005,CrystalBall,une enzyme artificielle pour une catalyse hétérogene(2014), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: Oxidase test, 010405 organic chemistry, Chemistry, catalysis-oxidation, reaction paths, chemistry.chemical_element, spin flip, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, DUAL (cognitive architecture), 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, computational chemistry, Catalysis, 0104 chemical sciences, Ruthenium, hydroxychlorination, Biocatalysis, epoxidation, artificial enzymes, Chemoselectivity, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract: International audience; Artificial enzymes represent an attractive alternative to design abiotic biocatalysis. EcNikA-Rul, an artificial metalloenzyme developed by embedding a ruthenium-based catalyst into the cavity of the periplasmic nickel-binding protein NikA, was found to efficiently and selectively transform certain alkenes. The objective of this study was to provide a rationale on the enzymatic function and the unexpected substrate-dependent chemoselectivity of EcNikA-Rul thanks to a dual experimental/computational study. We observed that the de novo active site allows the formation of the terminal oxidant via the formation of a ruthenium aquo species that subsequently reacts with the hypervalent iodine of phenyl iodide diacetic acid. The oxidation process relies on a Ru$^{IV}$=0 pathway via a two-step reaction with a radical intermediate, resulting in the formation of either a chlorohydrin or an epoxide. The results emphasize the impact of the protein scaffold on the kinetics of the reaction, through (i) the promotion of the starting oxidizing species via the exchange of a CO ligand with a water molecule; and (ii) the control of the substrate orientation on the intermediate structures, formed after the Ru$^{IV}$=0 attack. When a C alpha attack is preferred, chlorohydrins are formed while an attack on C beta leads to an epoxide. This work provides evidence that artificial enzymes mimic the behavior of their natural counterparts.
Published: 2020

42. Redox polyelectrolyte modified gold nanoparticles enhance the detection of adenosine in an electrochemical split‐aptamer assay

Author: Lucy L. Coria-Oriundo, Yoann Roupioz, Fernando Battaglini, Helena Ceretti, Instituto de Química Física de los Materiales, Medio Ambiente y Energía [Buenos Aires] (INQUIMAE), Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET)-Facultad de Ciencias Exactas y Naturales [Buenos Aires] (FCEyN), Universidad de Buenos Aires [Buenos Aires] (UBA)-Universidad de Buenos Aires [Buenos Aires] (UBA), Universidad Nacional de Ingeniería (UNI), Universidad Nacional de General Sarmiento [Los Polvorines, Buenos Aires] (UNGS), Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB ), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département Interfaces pour l'énergie, la Santé et l'Environnement (DIESE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)
Subjects: [SDV.BIO]Life Sciences [q-bio]/Biotechnology, Chemistry, Aptamer, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Polyelectrolyte, 0104 chemical sciences, Colloidal gold, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 0210 nano-technology, Nuclear chemistry
Abstract: International audience; We present an electrochemical sandwich‐type assay based on the splitting of an aptamer into two fragments. Gold nanoparticles are modified with one of the fragments and a redox polyelectrolyte. The first is used as the recognition element, while the other for the electrochemical signal generation. The split‐aptamer used here can detect adenosine, used as a model system for recognizing small molecules. The multiple binding sites on the nanoparticle, along with the high number of redox probes, yield a selective and sensitive assay for adenosine, achieving a limit of detection of 3.1 nM and a linear range up to 75 nM. The obtained results are analyzed in terms of the nanoparticle and electrode architectures. The assay can be easily extended to other small molecules and sandwich assays, representing a promising tool for detecting metabolites at the nanomolar level.
Published: 2020

43. Water-assisted photocatalytic sulfide and alcohol oxidation by a Ru-Ru dyad

Author: Klein, Johannes, Torelli, Stéphane, Jouvenot, Damien, Loiseau, Fredérique, Ménage, Stéphane, Hamelin, Olivier, Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), ANR-15-CE07-0025,TROICAT,Nouveaux procédés catalytiques propres : Photocatalyse d'oxydation utilisant l'eau et le dioxygène comme seules sources d'atome d'oxygène.(2015), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), GON, Nathalie, Grenoble, une chimie bio-motivée - - ARCANE2011 - ANR-11-LABX-0003 - LABX - VALID, CBH-EUR-GS - - CBH-EUR-GS2017 - ANR-17-EURE-0003 - EURE - VALID, and Nouveaux procédés catalytiques propres : Photocatalyse d'oxydation utilisant l'eau et le dioxygène comme seules sources d'atome d'oxygène. - - TROICAT2015 - ANR-15-CE07-0025 - AAPG2015 - VALID
Subjects: dyad, [SDV.EE]Life Sciences [q-bio]/Ecology, environment, [SDV.EE] Life Sciences [q-bio]/Ecology, environment, sulfide, education, [CHIM.CATA] Chemical Sciences/Catalysis, alcohol oxidation, [CHIM.CATA]Chemical Sciences/Catalysis, Photocatalysis
Abstract: International audience; Moving toward eco-friendly and ecoenvironmentally processes to perform specific organic transformations is more than ever at stake. Inspired by Nature that uses light as inducer with PSII, a new Rubased dyad combining a photosensitizer with a catalytic partner was developed. Upon irradiation with low power consumption blue LEDs, this system has proven its effectiveness during the catalytic oxidation of various sulfides and alcohols with water as unique oxygen atom source.
Published: 2020

44. Glucose oxidase bioanodes for glucose conversion and H2O2 production for horseradish peroxidase biocathodes in a flow through glucose biofuel cell design

Author: Olivier Ondel, Michael Holzinger, Caroline Abreu, Serge Cosnier, Alan Le Goff, François Buret, Yannig Nedellec, Ampère, Département Bioingénierie (BioIng), Ampère (AMPERE), École Centrale de Lyon (ECL), Université de Lyon-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-École Centrale de Lyon (ECL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Département de Chimie Moléculaire - Biosystèmes Electrochimiques et Analytiques (DCM - BEA), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Ampère, Département Energie Electrique (EE), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), platform Chimie NanoBio ICMG FR 2607 (PCN-ICMG), Institute Carnot PolyNat at Grenoble, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: H2O2, Energy Engineering and Power Technology, 02 engineering and technology, Electrolyte, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Horseradish peroxidase, law.invention, chemistry.chemical_compound, law, [CHIM]Chemical Sciences, Glucose oxidase, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Cellulose, biology, Renewable Energy, Sustainability and the Environment, Chemistry, Substrate (chemistry), 021001 nanoscience & nanotechnology, Biofuel cells, Cathode, 0104 chemical sciences, Anode, Glucose, Membrane, Flow stacks, Chemical engineering, biology.protein, 0210 nano-technology
Abstract: International audience; Bioelectrocatalytic carbon nanotube pellets comprising glucose oxidase (GOx) at the anode and horseradish peroxidase (HRP) at the cathode were integrated in a glucose/H2O2 flow-through fuel cell setup. The porous bioelectrodes, separated with a cellulose membrane, were assembled in a design allowing the fuel/electrolyte flow through the entire fuel cell with controlled direction. An air saturated 5 mmol L−1 glucose solution was directed through the anode where glucose is used for power conversion and for the enzymatic generation of hydrogen peroxide supplying the HRP biocathode with its substrate. This configuration showed an open circuit voltage (OCV) of 0.6 V and provided 0.7 ± 0.035 mW at 0.41 V. Furthermore, different charge/discharge cycles at 500 Ω and 3 kΩ were applied to show the long term stability of this setup producing 290 μW h (1.04 J) of energy after 48 h. The biofuel cell design further allows a convenient assembly of several glucose biofuel cells in reduced volumes and its connection in parallel or in series.
Published: 2018

45. Efficient Buchwald-Hartwig-Migita Cross-Coupling for DNA Thioglycoconjugation

Author: Océane Théry, Nicolas Probst, Samir Messaoudi, Rémy Lartia, Mouâd Alami, Eric Defrancq, Biomolécules : Conception, Isolement, Synthèse (BioCIS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Molécules bioactives, conception, isolement et synthèse (MBCIS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Timcal Belgium SA, Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Synthèse et étude de systèmes à intêret biologique (SEESIB), Université Blaise Pascal - Clermont-Ferrand 2 (UBP)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Clermont-Ferrand (ICCF), and Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-SIGMA Clermont (SIGMA Clermont)
Subjects: Spectrometry, Mass, Electrospray Ionization, Glycosylation, Oligonucleotides, chemistry.chemical_element, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Nucleobase, chemistry.chemical_compound, [CHIM]Chemical Sciences, DNA-glycoconjugates, thioglycoconjugation, Sulfhydryl Compounds, thiosaccharide, Chromatography, High Pressure Liquid, Pd catalysis, 010405 organic chemistry, Oligonucleotide, Organic Chemistry, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, Coupling (electronics), chemistry, Divergent synthesis, Palladium, DNA
Abstract: International audience; An efficient method for the thioglycoconjugation of iodinated oligonucleotides by Buchwald-Hartwig-Migita cross-coupling under mild conditions is reported. The method enables divergent synthesis of many different functionalized thioglycosylated ODNs in good yields, without affecting the integrity of the other A, C, and G nucleobases.
Published: 2018

46. Design of interpenetrating chitosan and poly(ethylene glycol) sponges for potential drug delivery applications

Author: Lisa Racine, Rachel Auzély-Velty, Guillaume Costa, Isabelle Texier, Eric Bayma-Pecit, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), ANR-15-IDEX-0002,UGA,IDEX UGA(2015), and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: Polymers and Plastics, Scanning electron microscope, Biocompatible Materials, macromolecular substances, 02 engineering and technology, Semi-interpenetrating network, 010402 general chemistry, 01 natural sciences, Polyethylene Glycols, Chitosan, [SPI]Engineering Sciences [physics], chemistry.chemical_compound, Drug Delivery Systems, Spectroscopy, Fourier Transform Infrared, Polymer chemistry, PEG ratio, Materials Chemistry, Poly(ethylene) glycol, Molecule, Fourier transform infrared spectroscopy, Organic Chemistry, technology, industry, and agriculture, Biomaterial, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, Sponges, Drug delivery, 0210 nano-technology, Ethylene glycol
Abstract: International audience; Semi-interpenetrating chitosan (CS)/poly(ethylene glycol) (PEG) sponges were designed by crosslinking PEG in the CS matrix via nucleophilic thiol-yne addition. This reaction does not require the use of any potentially cytotoxic catalytic species and offers possibilities to prepare materials with tunable properties. The molecular structure of the sponges was analyzed by FTIR spectroscopy, which provided evidence of intermolecular interactions between PEG and CS, and the presence of a cross-linked PEG network in the CS matrix. The crosslinked CS/PEG sponges displayed a structure with large interconnected pores (tens of micrometers) as demonstrated by scanning electron miscoscopy, in comparison to blended materials with irregular and smaller pores. The crosslinked sponges also exhibited improved mechanical properties (higher Young's modulus) and stability at physiological pH. All together, these interesting properties open the way for the application of this biomaterial in topical drug delivery.
Published: 2017

47. High yield production of Rhizobium NodB chitin deacetylase and its use for in vitro synthesis of lipo-chitinoligosaccharide precursors

Author: Chambon, Rémi, Pradeau, Stéphanie, Fort, Sébastien, Cottaz, Sylvain, Armand, Sylvie, Géoarchitecture : Territoires, Urbanisation, Biodiversité, Environnement, Université de Rennes (UR)-Université de Brest (UBO), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), ANR-11-LABX-0003-01, LABoratoires d’EXcellence ARCANE, Institut Carnot PolyNat, ENSA 2012-2017, Bill and Melinda Gates Foundation, ICMG, BioCOS 2010-2014, French Agence Nationale de la Recherche, ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université de Brest (UBO)
Subjects: Thin layer chromatography, TLC, Lipopolysaccharides, [SDV.BIO]Life Sciences [q-bio]/Biotechnology, [SDV]Life Sciences [q-bio], Sodium dodecyl sulfate polyacrylamide gel electrophoresis, SDS-PAGE, Immobilized Metal ion Affinity Chromatography, IMAC, Oligosaccharides, Chitinoligosaccharide deacetylated at non-reducing GlcNAc unit, CO(N), Chitin, Chitintetraose, CO-IV, Biochemistry, Article, Amidohydrolases, Analytical Chemistry, Lipo-chitinoligosaccharide, LCO, Thioredoxin, Trx, [CHIM]Chemical Sciences, Chitinbiose, CO-II, ComputingMilieux_MISCELLANEOUS, In vitro synthesis, Matrix-Assisted Laser Desorption/Ionization Time Of Flight Mass Spectrometry, MALDI-TOF MS, Chitinoligosaccharide, CO, Chitin deacetylase, CD, Molecular Structure, fungi, Organic Chemistry, food and beverages, NodB deacetylase, D-glucosamine, GlcN, Recombinant Proteins, Isopropyl β-D-thiogalactopyranoside, IPTG, Six histidine tag, His6 tag, High Performance Size Exclusion Chromatography, HPSEC, Lipo-chitinoligosaccharides, 1,4-dithiothreitol, DTT, N-acetyl-D-glucosamine, GlcNAc, Chitinpentaose, CO-V, Rhizobium
Abstract: Lipo-chitinoligosaccharides (LCOs) are key molecules for the establishment of plant-microorganisms symbiosis. Interactions of leguminous crops with nitrogen-fixing rhizobial bacteria involve Nod factors, while Myc-LCOs improve the association of most plants with arbuscular mycorrhizal fungi. Both Nod factors and Myc-LCOs are composed of a chitinoligosaccharide fatty acylated at the non-reducing end accompanied with various substituting groups. One straightforward way to access LCOs is starting from chitin hydrolysate, an abundant polysaccharide found in crustacean shells, followed by regioselective enzymatic cleavage of an acetyl group from the non-reducing end of chitin tetra- or pentaose, and subsequent chemical introduction of N-acyl group. In the present work, we describe the in vitro synthesis of LCO precursors on preparative scale. To this end, Sinorhizobium meliloti chitin deacetylase NodB was produced in high yield in E. coli as a thioredoxin fusion protein. The recombinant enzyme was expressed in soluble and catalytically active form and used as an efficient biocatalyst for N-deacetylation of chitin tetra- and pentaose., Graphical abstract Image 1, Highlights • Rhizobium NodB deacetylase is expressed and purified in active form in E. coli. • Yield optimization gives up to 100 mg of purified deacetylase from 1 L of culture medium. • In vitro synthesis of lipo-chitinoligosaccharides precursors is performed on preparative scale.
Published: 2017
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48. Electrochemical Characterizations of four Main Redox-metabolites ofPseudomonas Aeruginosa

Author: George G. Malliaras, Maxime Gougis, Julie Oziat, Pascal Mailley, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ecole Natl Super Mines, Dept Bioelect, Ecole Natl Super Mines Gardanne, and ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011)
Subjects: 0301 basic medicine, Electrochemical detection, medicine.disease_cause, Electrochemistry, 01 natural sciences, Redox, Analytical Chemistry, [SPI]Engineering Sciences [physics], 03 medical and health sciences, chemistry.chemical_compound, Pyocyanin, medicine, Metabolites detection, biology, 010405 organic chemistry, Pseudomonas aeruginosa, Quorum Sensing, biology.organism_classification, Combinatorial chemistry, 0104 chemical sciences, Pseudomonas quinolone signal, Quorum sensing, 030104 developmental biology, chemistry, Bacteria
Abstract: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Bacterial identification is of first importance in clinic nowadays. For few years, electrochemistry appears as a reliable route for characterizations outside of laboratories. Nowadays, researchers mainly focus on the opportunistic pathogen Pseudomonas aeruginosa because of its production of the Pyocyanin toxin which has an electrochemical case study behavior. Other P. aeruginosa secreted molecules are also studied in a lesser extent. This work deals with the systematic electrochemical characterizations in aprotic and protic solvents of 4 main metabolites of this bacterium in the view of multispecies detection of P. aeruginosa. We report here the behavior of the 2-Heptyl-4(1H)-quinolone (HHQ), Pseudomonas Quinolone Signal (PQS), Pyocyanin (PYO) and the 2′aminoacetophenone (2-AA). All the mentioned species are clearly visible by using electrochemical techniques (cyclic and square wave voltammetries). The 2 most suitable species for electrochemical detection appear to be PQS and PYO because of their detection at low potential.
Published: 2017

49. An oxime-based glycocluster microarray

Author: David Goyard, Eric Defrancq, Françoise Vinet, Olivier Renaudet, Antoine Hoang, Eugénie Laigre, Pascal Dumy, Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Ingéniérie et Intéractions BioMoléculaires (DCM - I2BM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), ANR-12-JS07-0001,VacSyn,Développement de Vaccins Synthétiques multiantigéniques antitumoraux(2012), European Project: 647938,H2020,ERC-2014-CoG,LEGO(2015), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Universitaire de France (IUF), and Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.)
Subjects: Microarray, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Carbohydrates, Molecular Conformation, Substrate (chemistry), Microarray Analysis, 010402 general chemistry, Oxime, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, Thermal oxide, Oximes, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, DNA microarray, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Carbohydrate microarrays represent powerful tools to study and detect carbohydratebinding proteins, pathogens or cells. In this paper, we report two original oximebased methods to prepare surfaces displaying well-defined structures and valency in a given microspot with improved recognition potency with lectins. In a first “direct” approach, fully synthetic aminooxylated glycoclusters have been coated onto aldehyde-activated SiO$_2$ (silicium substrate doped with 50 nm thermic oxide layer). To improve the preparation of the microarray in term of rapidity and simplicity and to provide addressable surfaces on which sugars can be linked chemoselectively as clusters at defined plots, a second “indirect” strategy has been developed using successive oxime ligation steps. In both cases, binding assays with labelled lectins have revealed more potent and selective interaction due to the clustered presentation of sugars. The observed differences of interaction have been confirmed in solution by ITC.
Published: 2017

50. Cyclotriveratrylene-Based Glycoclusters as High Affinity Ligands of Bacterial Lectins fromPseudomonas aeruginosaandBurkholderia ambifaria

Author: Jean-Pierre Dutasta, Alexandre Martinez, Zachary P. Michael, Sébastien Vidal, Alexander Star, Anne Imberty, Nicolas Galanos, Yanan Chen, Emilie Gillon, Chimie Organique 2-Glycochimie (CO2GLYCO), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches sur les Macromolécules Végétales (CERMAV ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Department of Chemistry, University of Pittsburgh, University of Pittsburg, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), ANR-11-LABX-0003,ARCANE,Grenoble, une chimie bio-motivée(2011), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Isothermal microcalorimetry, chemistry.chemical_classification, biology, 010405 organic chemistry, Glycoconjugate, Burkholderia ambifaria, Lectin, Cyclotriveratrylene, Context (language use), General Chemistry, 010402 general chemistry, biology.organism_classification, 01 natural sciences, Combinatorial chemistry, Fucose, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Click chemistry, biology.protein, [CHIM]Chemical Sciences, Organic chemistry
Abstract: International audience; The design of multivalent glycoconjugates has been largely studied using a variety of core scaffolds. Cyclotriveratrylenes (CTV) have been scarcely used in this context. The synthesis of the tri- and hexa-propargylated CTV cores allowed the prepn. of the corresponding glycoclusters with galactose or fucose residues through azide-alkyne "click" chem. Their interactions with bacterial lectins (LecA, LecB and BambL) was confirmed and studied by titrn. microcalorimetry. Adsorption onto carbon nanotubes was then attempted based on the hydrophobic CTV cores. Their incorporation into field effect transistor (FET) devices was accomplished but the data collected largely suggested a poor interaction of CTV-based glycoclusters with the carbon nanotubes leading to non-specific detection of the lectins.
Published: 2016

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